Catalyst systems for crystallizable reactor-grade resins.

Abstract

The present disclosure relates to a catalyst system for producing crystallizable polyester compositions containing residues of terephthalic acid, neopentyl glycol (NPG), 1,4-cyclohexanedimethanol (CHDM), ethylene glycol (EG), and diethylene glycol (DEG) in specific composition ranges that have particular advantages and improved properties, including recyclability.

Description

FIELD OF THE INVENTION

[0001] This disclosure relates to a catalyst system for producing crystallizable polyester compositions containing residues of terephthalic acid, neopentyl glycol (NPG), 1,4-cyclohexanedimethanol (CHDM), ethylene glycol (EG), and diethylene glycol (DEG) within a specific composition range that has certain advantages and improved properties, including recyclability. [Background technology]

[0002]

[0002] Polyester compositions containing certain glycols of moderate reactivity, such as neopentyl glycol (NPG; 2,2-dimethyl-1,3-propanediol), are well known and used in a variety of applications. However, these glycols are often less reactive in esterification reactions than other glycols, such as ethylene glycol (EG) and 1,4-cyclohexanedimethanol (CHDM), and the preparation of compositions incorporating these glycols may require extreme reaction conditions, excessively high loadings of glycols, specialized catalysts, staged addition of reactants, or some combination of these variables to achieve the desired product molecular weight at reasonable production efficiencies. Furthermore, the measures typically used to improve production efficiencies and glycol incorporation in compositions made from these glycols often result in high levels of glycol decomposition, poor product color, a population of undesirable polymer end groups, and poor incorporation of the glycol into polyesters produced in combination with other glycols.

[0003] Historically, titanium-only catalysts have been the catalyst of choice for the production of copolymerized polyester compositions formed from combinations of terephthalic acid (TPA), ethylene glycol (EG), 1,4-cyclohexanedimethanol (CHDM), and diethylene glycol (DEG). These catalyst systems typically contain 20-25 ppm titanium and 25 ppm phosphorus, which acts as a modifier. However, because of the presence of NPG in these compositions, these titanium-only systems were not suitable for the crystallizable polyester compositions of the present disclosure.

[0004] In the present disclosure, it has been discovered that crystallizable polyester compositions containing residues of terephthalic acid, neopentyl glycol (NPG), 1,4-cyclohexanedimethanol (CHDM), ethylene glycol (EG), and diethylene glycol (DEG) are recyclable in the PET recycling stream. The presence of NPG in these crystallizable polyester compositions necessitated the development of novel catalyst systems. Specifically, the color of the polyesters of the present disclosure is very high when prepared using a titanium-only catalyst system. * The polymer exhibited a yellow color (i.e., a very yellow color). Increasing the phosphorus loading, while slowing the polymerization rate, was ineffective in reducing the intense yellow color. Decreasing the titanium concentration only slightly improved the color, but still slowed the polymerization rate, as observed by monitoring the intrinsic viscosity achieved over time.

[0005] It has now been discovered that titanium-antimony catalyst systems, when used in combination with phosphorus compounds, can produce polyester compositions having significantly better color than compositions produced using titanium-only systems at the same or improved polymerization rates.

[0006]

[0006] There is a commercial need for crystallizable polyester compositions that can be recycled in the PET recycling stream and that exhibit superior performance characteristics. There is a commercial need for catalyst systems to produce crystallizable polyester compositions that have excellent polymerization rates and excellent color. Summary of the Invention

[0007] It has been discovered that specific combinations of glycol monomers can produce crystallizable polyester compositions that do not affect the recycling of the associated PET during recycling. Articles made with these crystallizable polyester resins are processed alongside PET articles, ultimately becoming components of the recyclable PET flakes that result from the recycling process. It has also been discovered that the selection of specific combinations of glycol monomers and their amounts are critical to producing crystallizable polyesters with superior performance properties. The optimal polyester resin compositions of the present disclosure are amorphous yet crystallizable. These compositions therefore exhibit excellent properties for applications such as film and sheet, including shrink film and thermoformable sheet, while possessing high strain-induced crystalline melting points, thereby providing compatibility with the recycling process. Articles made with the polyester compositions of the present disclosure do not need to be removed during the recycling process and do not affect the recycling process.

[0008]

[0008] It has further been found that catalyst systems containing low concentrations of titanium compounds in combination with antimony compounds and incorporating phosphorus compounds can produce crystallizable copolyester compositions containing neopentyl glycol with superior color and comparable reaction rates compared to conventional titanium-only systems incorporating phosphorus as a stabilizer / catalyst dampener. The low titanium-antimony combination is effective over a wide temperature range, allowing reaction temperatures in excess of 300°C to be used without sacrificing product color, even at the highest phosphorus concentrations disclosed.

[0009] In one embodiment, heat-shrinkable films made from the crystallizable polyester compositions of the present disclosure must meet various suitability-for-use criteria. The films must be strong, shrink in a controlled manner, and provide sufficient shrink force to hold the film against the bottle surface without crushing the contents. Furthermore, when these labels are fitted to polyester containers or bottles, these polyester shrink film labels must not interfere with the recycling process for the polyester containers or bottles. The shrink films of the present disclosure are advantageous because the labels can be recycled along with the bottles or containers. In this way, the entire container or bottle, including the label, can be recycled and converted into a new product without creating additional labor requirements or new environmental problems. Heat-shrinkable films have been manufactured from a variety of raw materials to meet a range of material requirements. This disclosure describes the unique and unexpected effects achieved by specific monomer combinations for shrink film resin compositions.

[0010] Polyester shrink film compositions have been used commercially as shrink film labels for food, beverages, personal care products, and household goods. Often, these shrink films are combined with clear polyethylene terephthalate (PET) bottles or containers. The entire container, including the bottle and label, is then sent for recycling. In a typical recycling center, PET and shrink film materials are processed together at the end of the process due to their similar composition and density. The PET flakes must be dried to remove any moisture remaining with the PET during the recycling process. Typically, PET is dried at temperatures exceeding 200°C. At these temperatures, typical polyester shrink film resins soften and become sticky, often clumping together with the PET flakes. These clumps must be removed prior to further processing. These clumps reduce the yield of PET flakes from the process and require additional handling steps. In one aspect of the present disclosure, clumping evaluation is performed using the APR Clumping Test: PET-S-08 "PET Flake Clumping Evaluation," revised November 16, 2018, and determination of recycle stream suitability is in accordance with Document No. PET-CG-02, "Critical Guidance Protocol for Clear PET Articles with Labels and Closures," dated April 11, 2019.

[0011]

[0011] In the present disclosure, it has been discovered that specific combinations of glycol monomers in polyester compositions can produce compositions with superior performance properties, and that these combinations are crystallizable so as not to affect the recyclability of PET. Furthermore, it has been discovered that specific combinations of glycol monomers in film or sheet resin compositions can produce films or sheets with superior performance properties, and that these combinations are crystallizable so as not to affect the recyclability of PET flakes. These crystallizable film or sheet resins can be processed with recycled PET and ultimately become components in the recyclable PET flakes that result from the recycling process. Furthermore, it has been discovered that the selection and amount of specific combinations of glycol monomers is important for producing films or sheets with superior performance properties and that are crystallizable. In other words, although the polyester compositions of the present disclosure are amorphous, they are "crystallizable" in the sense that they have a high strain-induced crystalline melting point. Therefore, these polyester compositions exhibit excellent properties in film or sheet applications, including shrink film, forming, thermoforming, or molding parts and / or articles, but also have high strain-induced crystalline melting points, so that when recycled PET flakes are subjected to high-temperature drying conditions, the crystallizable polyesters of the present disclosure do not form clumps that would interfere with normal mechanical operations such as flake cutting, drying, and feeding into an extruder for further processing into (recycled) polyester pellets, and can be recycled along with PET. Similarly, extruded sheets made from the resin compositions of the present disclosure do not need to be removed during the recycling process and therefore do not adversely affect the recycling process (e.g., https: / / www.thebalancesmb.com / recycling-polyethylene-terephthalate-pet-2877869 (See

[0012] One embodiment of the present disclosure is a crystallizable reactor-grade polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, wherein the (a) dicarboxylic acid component comprises (i) about 70 to about 100 mole % terephthalic acid residues, and (ii) about 0 to about 30 mole % aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises about 75 mole % or more ethylene glycol residues, and about 25 mole % or less other glycols, including one or more of: (i) about 0.1 to less than about 24 mole % neopentyl glycol residues, (ii) 0 to less than about 24 mole % 1,4-cyclohexanedimethanol residues, and (iii) about 1 to less than about 10 mole % total diethylene glycol residues in the final polyester composition, wherein the total mole % of the dicarboxylic acid component is 100 mole % and the total mole % of the diol component is 100 mole %.

[0013] One embodiment of the present disclosure is a crystallizable reactor-grade polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, wherein the (a) dicarboxylic acid component comprises (i) about 70 to about 100 mole % terephthalic acid residues, and (ii) 0 to about 30 mole % aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises about 80 mole % or more ethylene glycol residues, and about 20 mole % or less other glycols, including (i) about 5 to less than about 17 mole % neopentyl glycol residues, (ii) about 2 to less than about 10 mole % 1,4-cyclohexanedimethanol residues, and (iii) about 1 to less than about 5 mole % total diethylene glycol residues in the final polyester composition, wherein the total mole % of the dicarboxylic acid component is 100 mole % and the total mole % of the diol component is 100 mole %.

[0014]

[0014] One embodiment of the present disclosure is a crystallizable reactor-grade polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, wherein the (a) dicarboxylic acid component comprises (i) about 70 to about 100 mol % terephthalic acid residues, and (ii) about 0 to about 30 mol % aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises about 76 mol % or more ethylene glycol residues, and about 24 mol % or less amorphous content selected from (i) neopentyl glycol residues, (ii) cyclohexanedimethanol residues, and (iii) diethylene glycol residues in the final polyester composition, wherein the total mol % of the dicarboxylic acid component is 100 mol % and the total mol % of the diol component is 100 mol %.

[0015] One embodiment of the present disclosure is a crystallizable reactor-grade polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, wherein the (a) dicarboxylic acid component comprises (i) about 70 to about 100 mole % of terephthalic acid residues, and (ii) about 0 to about 30 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises (i) about 1 to about 30 mole % of neopentyl glycol residues, (ii) about 1 to less than about 30 mole % of 1,4-cyclohexanedimethanol residues, and (iii) about 1.5 to 6 mole % of diethylene glycol residues, wherein the remainder of the glycol component comprises (iv) ethylene glycol residues and (v) 0 to 20 mole % of at least one modified glycol residue, and the total mole % of the dicarboxylic acid component is 100 mole % and the total mole % of the diol component is 100 mole %.

[0016]

[0016] One embodiment of the present disclosure is a crystallizable reactor-grade polyester composition of any one of the preceding embodiments, wherein the reactor-grade polyester composition further comprises a catalyst system residue comprising 2 to 15 ppm titanium, 50 to 150 ppm antimony, and 0 to 60 ppm phosphorus, wherein the concentration of the catalyst system residue is based on the weight of the polyester.

[0017]

[0017] One embodiment of the present disclosure is a crystallizable reactor-grade polyester composition of any one of the preceding embodiments, wherein the reactor-grade polyester composition further comprises a catalyst system residue comprising 3 to 10 ppm titanium, 50 to 125 ppm antimony, and 0 to 50 ppm phosphorus, wherein the concentration of the catalyst system residue is based on the weight of the polyester.

[0018]

[0018] One embodiment of the present disclosure is a crystallizable reactor grade polyester composition of any one of the preceding embodiments, wherein the reactor grade polyester composition further comprises a catalyst system residue comprising 4 to 12 ppm titanium, 100 to 120 ppm antimony, and 2 to 50 ppm phosphorus, wherein the amount of catalyst system residue is based on the weight of the polyester.

[0019]

[0019] One embodiment of the present disclosure is a crystallizable reactor grade polyester composition of any of the preceding embodiments, which composition has a strain-induced crystalline melting point of 190°C or greater, or 200°C or greater.

[0020]

[0020] One embodiment of the present disclosure is a crystallizable reactor grade polyester composition of any of the preceding embodiments, which composition has a strain-induced crystalline melting point of 200°C or greater.

[0021] One embodiment of the present disclosure is a crystallizable polyester composition or crystallizable polyester blend comprising at least one polyester comprising (a) a dicarboxylic acid component, (b) a diol component, and (c) residues of a catalyst system, wherein the (a) dicarboxylic acid component comprises (i) about 70 to about 100 mole % of terephthalic acid residues, and (ii) about 0 to about 30 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises about 75 mole % or more of ethylene glycol residues, and about 25 mole % or less of other components, including one or more of: (i) about 0.1 to less than about 24 mole % of neopentyl glycol residues, (ii) about 0.1 to less than about 24 mole % of 1,4-cyclohexanedimethanol residues, and (iii) about 1 to less than about 10 mole % of total diethylene glycol residues in the final polyester composition. glycol, wherein the total mole % of the dicarboxylic acid components is 100 mole % and the total mole % of the diol components is 100 mole %, and the (c) catalyst system residue comprises 2 to 15 ppm titanium, 50 to 150 ppm antimony, and 0 to 60 ppm phosphorus, wherein the amount of the catalyst system residue is based on the weight of the polyester, or the (c) catalyst system residue consists essentially of 2 to 15 ppm titanium, 50 to 150 ppm antimony, and 0 to 60 ppm phosphorus, wherein the amount of the catalyst system residue is based on the weight of the polyester, or the (c) catalyst system residue consists of 2 to 15 ppm titanium, 50 to 150 ppm antimony, and 0 to 60 ppm phosphorus, wherein the amount of the catalyst system residue is based on the weight of the polyester, and the strain-induced crystalline melting point of the polyester is 190°C or higher or 200°C or higher.

[0021]

[0022] One embodiment of the present disclosure is a process for preparing a crystallizable reactor-grade polyester composition, the process comprising: (a) reacting a diacid component comprising terephthalic acid residues with a diol component comprising neopentyl glycol residues, 1,4-cyclohexanedimethanol residues, diethylene glycol residues, and ethylene glycol residues in the presence of 2 to 15 ppm of a titanium compound and 50 to 150 ppm of an antimony compound at an esterification reaction temperature of 240 to 270°C and a pressure of 5 to 50 psi to produce an esterified product; (b) prepolymerizing the esterified product in the presence of 0 to 60 ppm of a phosphorus stabilizer at a prepolymerization temperature of 255 to 275°C and a pressure of 200 to 500 mmHg to produce a polycondensation product; and (c) finishing the polycondensation product to produce a polyester, wherein the polyester has an intrinsic viscosity of at least 0.50 dL / g or 0.50 to 0.90 dL / g, and the polymerization temperature during the finishing treatment is increased to 280 to 320°C and the pressure is 0.3 to 7 mmHg.

[0022]

[0023] One embodiment of the present disclosure is a process for preparing a crystallizable reactor-grade polyester composition, the process comprising the steps of: (a) reacting a diacid component comprising terephthalic acid residues with a diol component comprising neopentyl glycol residues, 1,4-cyclohexanedimethanol residues, diethylene glycol residues, and ethylene glycol residues at an esterification reaction temperature of 240-270°C and a pressure of 5-50 psi to produce an esterification product; (b) treating the esterification product with an ester containing 2-15 ppm titanium; and (c) a step of pre-polymerizing the polycondensation product at a pre-condensation temperature of 255 to 275°C in the presence of an amine compound, 50 to 150 ppm of an antimony compound, and 0 to 90 ppm of a phosphorus stabilizer, to produce a polycondensation product by pre-polymerization; and (c) a step of finishing the polycondensation product to produce a polyester, wherein the polyester has an intrinsic viscosity of at least 0.50 dL / g or 0.50 to 0.90 dL / g, and the polymerization temperature during the finishing treatment is increased to 280 to 320°C and the pressure is 0.3 to 7 mmHg.

[0023]

[0024] An embodiment of the present disclosure is the process of any of the previous embodiments, wherein the polyester has excellent color or a b of 20 or less. * It has a value.

[0025] One embodiment of the present disclosure is a catalyst system for producing a crystallizable reactor-grade polyester composition, the system comprising 2 to 15 ppm of a titanium compound, 50 to 150 ppm of an antimony compound, and 0 to 90 ppm of a phosphorus compound, the polyester composition comprising terephthalic acid, 1,4-cyclohexanedimethanol, neopentyl glycol, ethylene glycol, and diethylene glycol.

[0024]

[0026] One embodiment of the present disclosure is a crystallizable film comprising a polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component, (b) a diol component, and (c) residues of a catalyst system, wherein the (a) dicarboxylic acid component comprises (i) about 70 to about 100 mole % of the residues of terephthalic acid, and (ii) about 0 to about 30 mole % of the residues of an aromatic and / or aliphatic dicarboxylic acid having up to 20 carbon atoms, and the (b) diol component comprises about 75 mole % or more of the residues of ethylene glycol, and (i) about 0.1 to less than about 24 mole % of the residues of neopentyl glycol. groups, (ii) from about 0.1 to less than about 24 mole % of 1,4-cyclohexanedimethanol residues, and (iii) from about 1 to less than about 10 mole % of total diethylene glycol residues in the final polyester composition, wherein the total mole % of dicarboxylic acid components is 100 mole % and the total mole % of diol components is 100 mole %, and wherein (c) the catalyst system residues include 2 to 15 ppm titanium, 50 to 150 ppm antimony, and 0 to 60 ppm phosphorus, wherein the concentration of the catalyst system residues is based on the weight of the polyester.

[0025]

[0027] One embodiment of the present disclosure is a crystallizable film comprising a polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component, (b) a diol component, and (c) residues of a catalyst system, wherein the (a) dicarboxylic acid component comprises (i) about 70 to about 100 mole % of terephthalic acid residues, and (ii) about 0 to about 30 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises about 75 mole % or more of ethylene glycol residues, and (i) 0 to less than about 24 mole % of neopentyl glycol residues. (ii) from about 0 to less than about 24 mole % of 1,4-cyclohexanedimethanol residues, and (iii) from about 1 to less than about 10 mole % of total diethylene glycol residues in the final polyester composition, wherein the total mole % of dicarboxylic acid components is 100 mole % and the total mole % of diol components is 100 mole %, and the (c) catalyst system residues include 2 to 15 ppm titanium, 50 to 150 ppm antimony, and 0 to 60 ppm phosphorus, wherein the concentration of catalyst system residues is based on the weight of the polyester.

[0026]

[0028] One embodiment of the present disclosure is a crystallizable film comprising a polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component, (b) a diol component, and (c) residues of a catalyst system, wherein the (a) dicarboxylic acid component comprises (i) about 70 to about 100 mole % of the residues of terephthalic acid, and (ii) about 0 to about 30 mole % of the residues of an aromatic and / or aliphatic dicarboxylic acid having up to 20 carbon atoms, and the (b) diol component comprises about 75 mole % or more of the residues of ethylene glycol, and (i) about 0.1 to less than about 24 mole % of the residues of neopentyl glycol. groups, (ii) from about 0.1 to less than about 24 mole % of 1,4-cyclohexanedimethanol residues, and (iii) from about 1 to less than about 10 mole % of total diethylene glycol residues in the final polyester composition, wherein the total mole % of dicarboxylic acid components is 100 mole % and the total mole % of diol components is 100 mole %, and wherein (c) the catalyst system residues include 2 to 15 ppm titanium, 50 to 150 ppm antimony, and 0 to 60 ppm phosphorus, wherein the concentration of the catalyst system residues is based on the weight of the polyester.

[0027]

[0029] One embodiment of the present disclosure is a crystallizable film comprising a polyester composition including at least one polyester comprising (a) a dicarboxylic acid component, (b) a diol component, and (c) residues of a catalyst system, wherein the (a) dicarboxylic acid component comprises (i) about 70 to about 100 mole % residues of terephthalic acid, and (ii) about 0 to about 30 mole % residues of aromatic and / or aliphatic dicarboxylic acids having up to 20 carbon atoms, and the (b) diol component comprises about 80 mole % or more residues of ethylene glycol, and (ii) about 5 to less than about 17 mole % residues of neopentyl glycol. (ii) from about 2 to less than about 10 mole % of 1,4-cyclohexanedimethanol residues, and (iii) from about 1 to less than about 5 mole % of total diethylene glycol residues in the final polyester composition, wherein the total mole % of dicarboxylic acid components is 100 mole % and the total mole % of diol components is 100 mole %, and the (c) catalyst system residues include 2 to 15 ppm titanium, 50 to 150 ppm antimony, and 0 to 60 ppm phosphorus, wherein the concentration of catalyst system residues is based on the weight of the polyester.

[0028]

[0030] One embodiment of the present disclosure is a crystallizable film comprising a polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component, (b) a diol component, and (c) residues of a catalyst system, wherein the (a) dicarboxylic acid component comprises (i) about 70 to about 100 mole % of the residues of terephthalic acid, and (ii) about 0 to about 30 mole % of the residues of an aromatic and / or aliphatic dicarboxylic acid having up to 20 carbon atoms, and the (b) diol component comprises about 76 mole % or more of the residues of ethylene glycol, and (i (ii) neopentyl glycol residues, (ii) cyclohexanedimethanol residues, and (iii) an amorphous content of about 24 mole % or less including diethylene glycol residues in the final polyester composition, wherein the total mole % of the dicarboxylic acid components is 100 mole % and the total mole % of the diol components is 100 mole %, and the (c) catalyst system residues include 2 to 15 ppm titanium, 50 to 150 ppm antimony, and 0 to 60 ppm phosphorus, wherein the concentration of the catalyst system residues is based on the weight of the polyester.

[0029]

[0031] One embodiment of the present disclosure is a crystallizable film comprising a polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component, (b) a diol component, and (c) residues of a catalyst system, wherein the (a) dicarboxylic acid component comprises (i) from about 70 to about 100 mole % of the residues of terephthalic acid, and (ii) from about 0 to about 30 mole % of the residues of an aromatic and / or aliphatic dicarboxylic acid having up to 20 carbon atoms, and the (b) diol component comprises (i) from about 1 to about 30 mole % of the residues of neopentyl glycol, whether formed in situ or not, (ii) from about 1 to about 30 mole % of the residues of a dicarboxylic acid having up to 20 carbon atoms. and (iii) about 1.5-6 mole % diethylene glycol residues, the remainder of the glycol component comprising (iv) ethylene glycol residues and (v) 0-10 mole % of at least one modified glycol residue, wherein the total mole % of the dicarboxylic acid components is 100 mole % and the total mole % of the diol components is 100 mole %, and the (c) catalyst system residue comprises 2-15 ppm titanium, 50-150 ppm antimony, and 0-60 ppm phosphorus, wherein the concentration of the catalyst system residue is based on the weight of the polyester.

[0030]

[0032] One embodiment of the present disclosure is a crystallizable film of any of the previous embodiments, wherein the film is stretched in at least one direction, the stretched film having a melting point of strain-induced crystals of 190° C. or greater.

[0031]

[0033] One embodiment of the present disclosure is a crystallizable film of any of the previous embodiments, wherein the film is stretched in at least one direction, the stretched film having a melting point of strain-induced crystals of 200° C. or greater.

[0032]

[0034] One embodiment of the present disclosure is a crystallizable film of any of the previous embodiments, wherein the film is stretched in at least one direction, and the stretched film has a melting point of strain-induced crystals of 190 to 200°C.

[0033]

[0035] One embodiment of the present disclosure is an extruded or calendered film comprising the crystallizable film of any of the previous embodiments.

[0036] One embodiment of the present disclosure is a thermoformable sheet comprising a polyester composition including at least one polyester comprising (a) a dicarboxylic acid component, (b) a diol component, and (c) the residue of a catalyst system, wherein the (a) dicarboxylic acid component comprises (i) from about 70 to about 100 mole % of the residues of terephthalic acid, and (ii) from about 0 to about 30 mole % of the residues of an aromatic and / or aliphatic dicarboxylic acid having up to 20 carbon atoms, and the (b) diol component comprises at least about 75 mole % of the residues of ethylene glycol, and (i) from about 0.1 to less than about 24 mole % of the residues of neopentyl glycol; (ii) from about 0.1 to less than about 24 mole % of 1,4-cyclohexanedimethanol residues, and (iii) from about 1 to less than about 10 mole % of total diethylene glycol residues in the final polyester composition, including about 25 mole % or less of other glycols, including one or more of the total diethylene glycol residues, wherein the total mole % of the dicarboxylic acid components is 100 mole % and the total mole % of the diol components is 100 mole %, and wherein (c) the catalyst system residues include 2 to 15 ppm titanium, 50 to 150 ppm antimony, and 0 to 60 ppm phosphorus, wherein the concentration of the catalyst system residues is based on the weight of the polyester.

[0034]

[0037] One embodiment of the present disclosure is a thermoformable sheet having a thickness of about 0.25 mm to about 6.4 mm comprising a polyester composition including at least one polyester comprising (a) a dicarboxylic acid component, (b) a diol component, and (c) the residue of a catalyst system, wherein the (a) dicarboxylic acid component comprises (i) about 70 to about 100 mole % residues of terephthalic acid, and (ii) about 0 to about 30 mole % residues of aromatic and / or aliphatic dicarboxylic acids having up to 20 carbon atoms, and the (b) diol component comprises about 80 mole % or more residues of ethylene glycol, and (i) about 5 to about 17 mole % or less of neopen (ii) from about 2 to less than about 10 mole % of 1,4-cyclohexanedimethanol residues, and (iii) from about 1 to less than about 5 mole % of total diethylene glycol residues in the final polyester composition, wherein the total mole % of the dicarboxylic acid components is 100 mole % and the total mole % of the diol components is 100 mole %, and wherein (c) the catalyst system residues comprise 2 to 15 ppm titanium, 50 to 150 ppm antimony, and 0 to 60 ppm phosphorus, wherein the concentration of the catalyst system residues is based on the weight of the polyester.

[0035]

[0038] One embodiment of the present disclosure is a thermoformable sheet having a thickness of about 0.25 mm to about 6.4 mm comprising a polyester composition including at least one polyester comprising (a) a dicarboxylic acid component, (b) a diol component, and (c) the residue of a catalyst system, wherein the (a) dicarboxylic acid component comprises (i) about 70 to about 100 mole % of the residues of terephthalic acid, and (ii) about 0 to about 30 mole % of the residues of an aromatic and / or aliphatic dicarboxylic acid having up to 20 carbon atoms; and the (b) diol component comprises about 76 mole % or more of the residues of ethylene glycol; and an amorphous content of about 24 mole % or less comprising one or more of (i) neopentyl glycol residues, (ii) cyclohexanedimethanol residues, and (iii) diethylene glycol residues in the final polyester composition, wherein the total mole % of the dicarboxylic acid components is 100 mole % and the total mole % of the diol components is 100 mole %, and the (c) catalyst system residues include 2 to 15 ppm titanium, 50 to 150 ppm antimony, and 0 to 60 ppm phosphorus, wherein the concentration of the catalyst system residues is based on the weight of the polyester.

[0036]

[0039] One embodiment of the present disclosure is a thermoformable sheet having a thickness of about 0.25 mm to about 6.4 mm comprising a polyester composition including at least one polyester comprising (a) a dicarboxylic acid component, (b) a diol component, and (c) the residue of a catalyst system, wherein the (a) dicarboxylic acid component comprises (i) about 70 to about 100 mole % of the residues of terephthalic acid, and (ii) about 0 to about 30 mole % of the residues of an aromatic and / or aliphatic dicarboxylic acid having up to 20 carbon atoms, and the (b) diol component, whether formed in situ or not, comprises (i) about 1 to about 30 mole % of the residues of neopentyl glycol, (ii) about 1 to about 30 mole % of the residues of a terephthalic acid, and (iii) about 1 to about 30 mole % of the residues of a terephthalic acid, and (iii) from about 1.5 to about 6 mole % of diethylene glycol residues, the remainder of the glycol component comprising (iv) ethylene glycol residues and (v) optionally 0 to 10 mole % or 0 to 5 mole % of at least one modified glycol residue, wherein the total mole % of the dicarboxylic acid components is 100 mole % and the total mole % of the diol components is 100 mole %, and the (c) catalyst system residue comprises 2 to 15 ppm titanium, 50 to 150 ppm antimony, and 0 to 60 ppm phosphorus, wherein the concentration of the catalyst system residue is based on the weight of the polyester.

[0037]

[0040] An embodiment of the present disclosure is a formed, thermoformed, or molded article comprising or prepared from a sheet of any of the preceding embodiments, wherein the sheet has a strain-induced crystalline melting point of 190°C or greater.

[0038]

[0041] An embodiment of the present disclosure is a formed, thermoformed, or molded article comprising or prepared from a sheet of any of the preceding embodiments, the sheet having a strain-induced crystalline melting point of 200° C. or greater.

[0039]

[0042] One embodiment of the present disclosure is a formed, thermoformed, or molded article comprising or prepared from a sheet of any of the preceding embodiments, the sheet having a strain-induced crystalline melting point of 190°C to 215°C.

[0040]

[0043] One embodiment of the present disclosure is a formed, thermoformed, or molded article comprising or prepared from a sheet of any of the preceding embodiments.

[0044] One embodiment of the present disclosure is an article selected from medical device packaging, medical related packaging, healthcare product packaging, commercial food supply products, trays, containers, food plates, tumblers, storage bins, bottles, cookware, blenders and mixing bowls, household items, water bottles, vegetable trays, dishwasher parts, refrigerator parts, vacuum cleaner parts, ophthalmic lenses, and frames or toys comprising or prepared from a sheet of any of the preceding embodiments.

[0041]

[0045] One embodiment of the present disclosure is a method of making a formed or thermoformed article or part from a sheet of any of the previous embodiments, the method comprising the steps of: A) heating a sheet comprising a polyester composition of the present disclosure; B) applying air pressure, vacuum, and / or physical pressure to the heat-softened sheet; C) conforming the sheet to the shape of a mold by vacuum or pressure; D) cooling the sheet to a temperature below its Tg; and E) removing the formed or thermoformed part or article from the mold.

[0042]

[0046] One embodiment of the present disclosure is a polyester recycling process stream comprising recycled polyethylene terephthalate flakes mixed together with at least about 0.1% by weight of the crystallizable recycled shrink film of the present disclosure.

[0043]

[0047] One embodiment of the present disclosure is a polyester recycling process stream comprising recycled polyethylene terephthalate flakes mixed together with at least about 0.1 wt. % of the crystallizable reactor grade polyester composition of the present disclosure.

[0044]

[0048] One embodiment of the present disclosure is a polyester recycling process stream comprising recycled polyethylene terephthalate flakes mixed together with at least about 0.1% by weight of the crystallizable recycled thermoformable sheet of the present disclosure.

[0045]

[0049] One embodiment of the present disclosure is a polyester recycling process stream comprising recycled polyethylene terephthalate flakes mixed together with at least about 0.1% by weight of the crystallizable recycled shrink film of the present disclosure, wherein the stream passes the Association for Plastic Recyclers (APR) test item PET-CG-02.

[0046]

[0050] Thus, the crystallizable composition of the present disclosure is provided as a convenient component of a PET recycling stream, so long as the composition accompanies the PET in the recycling stream without the need for an additional separation step. Accordingly, in one embodiment of the present disclosure, a polyester recycling process stream is provided that includes recycled polyethylene terephthalate flakes having at least about 0.1% by weight of the crystallizable composition of the present disclosure mixed therewith. In another embodiment, the stream has passed Document No. PET-CG-02, "Key Instructions for Transparent PET Articles with Labels and Seals," dated April 11, 2019.

[0047]

[0051] One embodiment of the present disclosure is a crystallizable polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component, (b) a diol component, and (c) residues of a catalyst system, wherein the (a) dicarboxylic acid component comprises (i) about 70 to about 100 mole % of terephthalic acid residues, and (ii) about 0 to about 30 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises about 75 mole % or more of ethylene glycol residues, and about 25 mole % or less of other glycols, including one or more of: (i) about 0.1 to less than about 24 mole % of neopentyl glycol residues, (ii) about 0.1 to less than about 24 mole % of 1,4-cyclohexanedimethanol residues, and (iii) about 1 to less than about 10 mole % of total diethylene glycol residues in the final polyester composition; wherein the total mole % of the dicarboxylic acid components is 100 mole % and the total mole % of the diol components is 100 mole %, and the (c) catalyst system residue comprises 2 to 15 ppm titanium, 50 to 150 ppm antimony, and 0 to 60 ppm phosphorus, wherein the amount of the catalyst system residue is based on the weight of the polyester; or the (c) catalyst system residue consists essentially of 2 to 15 ppm titanium, 50 to 150 ppm antimony, and 0 to 60 ppm phosphorus, wherein the amount of the catalyst system residue is based on the weight of the polyester; or the (c) catalyst system residue consists of 2 to 15 ppm titanium, 50 to 150 ppm antimony, and 0 to 60 ppm phosphorus, wherein the amount of the catalyst system residue is based on the weight of the polyester; and the strain-induced crystalline melting point of the polyester is 190°C or higher or 200°C or higher. [Brief explanation of the drawings]

[0048] [Figure 1]

[0052] Figure 1 shows PET agglomeration (%) versus relative crystallinity. Triangular dots indicate PET agglomeration greater than 1%. Circle dots indicate PET agglomeration less than 1%, thus passing Document No. PET-CG-02, "Important Instructions for Transparent PET Articles with Labels and Seals," dated April 11, 2019. Detailed Description of the Invention

[0049]

[0053] The present disclosure will be better understood by reference to the following detailed description of certain embodiments and examples of the present disclosure. In accordance with the purposes of this disclosure, certain embodiments of the present disclosure are described in the Summary of the Invention and further described herein below. Other embodiments of the present disclosure are also described herein.

[0050]

[0054] In the present disclosure, it has been discovered that a specific combination of glycol monomers in a polyester composition can produce a crystallizable polyester resin with excellent performance properties, and because the resin is crystallizable, it does not affect the recyclability of PET flakes during the recycling process. Articles such as shrink films and thermoformable sheets made using the crystallizable resins of the present disclosure can be processed with PET bottles and ultimately become a component in the recyclable PET flakes generated from the recycling process. Furthermore, it has been discovered that the selection and amount of the specific combination of glycol monomers is important for producing articles such as films or sheets, such as shrink films, that have excellent performance properties and are crystallizable.

[0051]

[0055] As used herein, the term "polyester" is intended to include "copolyesters" and is understood to mean a synthetic polymer prepared by the reaction of one or more difunctional and / or polyfunctional carboxylic acids with one or more difunctional and / or polyfunctional hydroxyl compounds, such as branching agents. Typically, the difunctional carboxylic acid may be a dicarboxylic acid, and the difunctional hydroxyl compound may be a dihydric alcohol, such as glycols and diols. The term "glycol" as used herein includes, but is not limited to, diols, glycols, and / or polyfunctional hydroxyl compounds, such as branching agents. Alternatively, the difunctional carboxylic acid may be a hydroxycarboxylic acid, such as p-hydroxybenzoic acid, and the difunctional hydroxyl compound may have an aromatic nucleus bearing two hydroxyl substituents, such as hydroquinone. As used herein, the term "residue" refers to any organic structure incorporated into a polymer by polycondensation and / or esterification reactions from the corresponding monomers. As used herein, the term "repeating unit" refers to an organic structure having a dicarboxylic acid residue and a diol residue linked via an ester group. Thus, for example, the dicarboxylic acid residue may be derived from a dicarboxylic acid monomer or its associated acid halides, esters, salts, anhydrides, and / or mixtures thereof. Furthermore, as used herein, the term "diacid" includes polyfunctional acids, such as branching agents. Thus, as used herein, the term "dicarboxylic acid" is intended to include dicarboxylic acids useful in the reaction step with a diol to produce a polyester, as well as any derivatives of the dicarboxylic acid, such as its associated acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, and / or mixtures thereof. As used herein, the term "terephthalic acid" is intended to include terephthalic acid itself and its residues, as well as any derivatives of terephthalic acid, such as its associated acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, and / or mixtures or residues thereof, useful in the reaction step with a diol to produce a polyester.

[0052]

[0056] The polyesters used in the present disclosure can typically be prepared from dicarboxylic acids and diols that react in substantially equal proportions and are incorporated into the polyester polymer as their corresponding residues. Thus, the polyesters of the present disclosure may contain substantially equimolar ratios of acid residues (100 mol%) and diol (and / or polyfunctional hydroxyl compound) residues (100 mol%), such that the total number of moles of repeat units equals 100 mol%. Thus, the mole percentages given in the present disclosure may be based on the total number of moles of acid residues, the total number of moles of diol residues, or the total number of moles of repeat units. For example, a polyester containing 10 mol% isophthalic acid, based on the total acid residues, means that the polyester contains 10 mol% isophthalic acid residues out of 100 mol% total acid residues. Thus, there will be 10 moles of isophthalic acid residues for every 100 moles of acid residues. As another example, a polyester containing 25 mole percent 1,4-cyclohexanedimethanol, based on total diol residues, means that the polyester contains 25 mole percent 1,4-cyclohexanedimethanol residues out of 100 mole percent total diol residues. Thus, there are 25 moles of 1,4-cyclohexanedimethanol residues for every 100 moles of diol residues.

[0053]

[0057] In certain embodiments, terephthalic acid or its esters, such as dimethyl terephthalate or mixtures of terephthalic acid residues and their esters, may comprise some or all of the dicarboxylic acid components used to produce polyesters useful in the present disclosure. In certain embodiments, terephthalic acid residues may comprise some or all of the dicarboxylic acid components used to produce polyesters useful in the present disclosure. For purposes of this disclosure, the terms "terephthalic acid" and "dimethyl terephthalate" are used interchangeably herein. In one embodiment, dimethyl terephthalate comprises some or all of the dicarboxylic acid components used to produce polyesters useful in the present disclosure. In some embodiments, 70 to 100 mol%, or 80 to 100 mol%, or 90 to 100 mol%, or 99 to 100 mol%, or 100 mol% terephthalic acid and / or dimethyl terephthalate and / or mixtures thereof may be used.

[0054]

[0058] In addition to terephthalic acid, the dicarboxylic acid component of the polyesters useful in the present disclosure may include up to 30 mol%, up to 20 mol%, up to 10 mol%, up to 5 mol%, or up to 1 mol% of one or more modified aromatic dicarboxylic acids. Yet another embodiment includes 0 mol% modified aromatic dicarboxylic acids. It is therefore contemplated that, when present, the amount of one or more modified aromatic dicarboxylic acids may range from any of these aforementioned endpoints, e.g., 0.01-10 mol%, 0.01-5 mol%, and 0.01-1 mol%. In one embodiment, modified aromatic dicarboxylic acids that may be used in the present disclosure include, but are not limited to, dicarboxylic acids having up to 20 carbon atoms and which may be linear, para-oriented, or symmetrical. Examples of modified aromatic dicarboxylic acids that may be used in the present disclosure include, but are not limited to, isophthalic acid, 4,4'-biphenyldicarboxylic acid, 1,4-, 1,5-, 2,6-, 2,7-naphthalenedicarboxylic acid, and trans-4,4'-stilbene dicarboxylic acid, and esters thereof. In one embodiment, the modified aromatic dicarboxylic acid is isophthalic acid.

[0055]

[0059] The carboxylic acid component of the polyesters useful in the present disclosure may be further modified with up to 10 mol%, e.g., up to 5 mol%, or up to 1 mol% of one or more aliphatic dicarboxylic acids containing 2 to 16 carbon atoms, such as cyclohexanedicarboxylic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and / or dodecanedioic dicarboxylic acid. Particular embodiments may also include 0.01 to 10 mol%, e.g., 0.1 to 10 mol%, 1 to 10 mol%, or 5 to 10 mol% of one or more modified aliphatic dicarboxylic acids. Yet other embodiments include 0 mol% modified aliphatic dicarboxylic acids. The total mol% of the dicarboxylic acid component is 100 mol%. In one embodiment, adipic acid and / or glutaric acid are provided in the modified aliphatic dicarboxylic acid component of the polyesters useful in the present disclosure.

[0056]

[0060] Esters of terephthalic acid and other modified dicarboxylic acids, or their corresponding esters and / or salts, may be used in place of the dicarboxylic acids. Suitable examples of dicarboxylic acid esters include, but are not limited to, dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, and diphenyl esters. In one embodiment, the ester is selected from at least one of methyl, ethyl, propyl, isopropyl, and phenyl esters.

[0057]

[0061] In one embodiment, the diol component of the crystallizable polyester compositions useful in the present disclosure may comprise 1,4-cyclohexanedimethanol. In another embodiment, the diol component of the crystallizable polyester compositions useful in the present disclosure may comprise 1,4-cyclohexanedimethanol and 1,3-cyclohexanedimethanol. The molar ratio of cis / trans 1,4-cyclohexanedimethanol may vary from 50 / 50 to 0 / 100, for example, from 40 / 60 to 20 / 80.

[0058]

[0062] In certain embodiments, the diol component of the crystallizable polyester compositions useful in the present disclosure may be, but is not limited to, 1 to 30 mol%, or 1 to 25 mol%, or 1 to 20 mol%, or 1 to 15 mol%, or 1 to 10 mol%, or 2 to 30 mol%, or 2 to 25 mol%, or 2 to 20 mol%, or 2 to 15 mol%, or 2 to 10 mol%, or 3 to 30 mol%, or 3 to 25 mol%, or 3 to 20 mol%, or 3 to 15 mol%, or 3 to 10 mol%, or 4 to 30 mol%, or 4 to 25 mol%, or 4 to 20 mol%, or 4 to 15 mol%, or 4 to 10 mol%, or 5 to 30 mol%, or 5 to 25 mol%, or 5 to 20 mol%, or 5 to 15 mol%, or 5 to 10 mol% of 1,4-cyclohexanedimethanol residues plus neopentyl glycol residues in the final polyester composition. or 6 to 30 mol%, or 6 to 25 mol%, or 6 to 20 mol%, or 6 to 15 mol%, or 6 to 10 mol%, or 7 to 30 mol%, or 7 to 25 mol%, or 7 to 20 mol%, or 7 to 15 mol%, or 7 to 10 mol%, or 8 to 30 mol%, or 8 to 25 mol%, or 8 to 20 mol%, or 8 to 15 mol%, or 8 to 10 mol%, or 9 to 30 mol%, or 9 to 25 mol%, or 9 to 20 mol%, or 9 to 15 mol%, or 9 to 10 mol%, or 10 to 30 mol%, or 10 to 25 mol%, or 10 to 20 mol%, or 10 to 15 mol%, or 11 to 30 mol%, or 11 to 25 mol%, 11 to 20 mol%, or 11 to 15 mol%, or 12 to 30 mol%, 12 to 25 mol%, or 12 to 20 mol%, 12 to 15 mol%, or 13 to 30 mol%, or 13 to 25 mol%, 13 to 20 mol%, or 13 to 15 mol%, 14 to 30 mol%, or 14 to 25 mol%, or 14 to 20 mol%, or 14 to 15 mol%, or 15 to 30 mol%.The composition may include a composition in which the mol% is 15 to 25 mol%, or 15 to 20 mol%, or 16 to 20 mol%, or 18 to 20 mol%, or 10 to 18 mol%, or 16 to 18 mol%, or 12 to 16 mol%, or 16 to 20 mol%, or 14 to 18 mol%, or 11 to 30 mol%, or 13 to 30 mol%, or 14 to 30 mol%, or 10 to 29 mol%, or 11 to 29 mol%, or 12 to 29 mol%, or 13 to 29 mol%, or 14 to 29 mol%, or 15 to 29 mol%, or 10 to 28 mol%, or 11 to 28 mol%, or 12 to 28 mol%, or 13 to 28 mol%, or 14 to 28 mol%, or 15 to 28 mol%. In one embodiment, the sum of 1,4-cyclohexanedimethanol residues and neopentyl glycol residues in the final polyester composition can be 1 to 16 mol %, 2 to 14 mol %, 4 to 15 mol %, or 2 to 21 mol %, or 2 to less than 20 mol %, or 4 to 20 mol %, or 5 to 18 mol %, or 10 to 21 mol %, or 12 to 21 mol %, where the total mol % of the diol component is 100 mol %.

[0059]

[0063] In one embodiment, the diol component of the crystallizable polyester compositions useful in the present disclosure may comprise 0 to 30 mol % neopentyl glycol, based on the total mol % of the diol component being 100 mol %. In one embodiment, the diol component of the crystallizable polyester compositions useful in the present disclosure may comprise 0.1 to 30 mol % neopentyl glycol, based on the total mol % of the diol component being 100 mol %. In one embodiment, the diol component of the crystallizable polyester compositions useful in the present disclosure may comprise 1 to 30 mol % neopentyl glycol, based on the total mol % of the diol component being 100 mol %. In one embodiment, the diol component of the crystallizable polyester compositions useful in the present disclosure may comprise 1 to 25 mol % neopentyl glycol, based on the total mol % of the diol component being 100 mol %. In one embodiment, the diol component of the crystallizable polyester compositions useful in the present disclosure may comprise 1 to 17 mol % neopentyl glycol, based on the total mol % of the diol component being 100 mol %. In one embodiment, the diol component of the crystallizable polyester compositions useful in the present disclosure may comprise 5 to 20 mol % neopentyl glycol, based on the total mol % of the diol component being 100 mol %. In one embodiment, the diol component of the crystallizable polyester compositions useful in the present disclosure may comprise 10 to 20 mol % neopentyl glycol, based on the total mol % of the diol component being 100 mol %. In one embodiment, the diol component of the crystallizable polyester compositions useful in the present disclosure may comprise 10 to 15 mol % neopentyl glycol, based on the total mol % of the diol component being 100 mol %. In one embodiment, the diol component of the crystallizable polyester composition useful in the present disclosure may comprise 15 to 25 mole % neopentyl glycol, based on the total mole % of the diol component being 100 mole %.

[0060]

[0064] In one embodiment, the diol component of the crystallizable polyester composition useful in the present disclosure is present in an amount of 0 to 30 mol%, or 0.01 to 30 mol%, or 1 to 30 mol%, or 2 to 30 mol%, or 0 to 20 mol%, or 0.1 to 20 mol%, or 1 to 20 mol%, or 2 to 20 mol%, or 0 to 15 mol%, or 0.01 to 15 mol%, or 1 to 15 mol%, or 2 to 15 mol%, or 0.01 to 14 mol%, or 0.01 to 13 mol%, or 0.01 to 12 mol%, or 0.01 to 11 mol%, or 0.01 to 10 mol%, based on the total mol% of the diol component being 100 mol%. %, or 0.01 to 9 mol%, or 0.01 to 8 mol%, or 0.01 to 7 mol%, or 0.01 to 6 mol%, or 0.01 to 5 mol%, or 3 to 15 mol%, or 3 to 14 mol%, or 3 to 13 mol%, or 3 to 12 mol%, or 3 to 11 mol%, or 3 to 10 mol%, or 3 to 9 mol%, or 3 to 8 mol%, or 3 to 7 mol%, or 2 to 10 mol%, or 2 to 9 mol%, or 2 to 8 mol%, or 2 to 7 mol%, or 2 to 5 mol%, or 1 to 7 mol%, or 1 to 5 mol%, or 1 to 3 mol% of 1,4-cyclohexanedimethanol residues.

[0061]

[0065] In one embodiment, the diol component of a polyester composition useful in the present disclosure may comprise 0.01 to 15 mol % of 1,4-cyclohexanedimethanol, based on the total mole % of the diol component being 100 mol %. In one embodiment, the diol component of a polyester composition useful in the present disclosure may comprise 0 to less than 15 mol % of 1,4-cyclohexanedimethanol, based on the total mole % of the diol component being 100 mol %. In one embodiment, the diol component of a polyester composition useful in the present disclosure may comprise 0.01 to 10 mol % of 1,4-cyclohexanedimethanol, based on the total mole % of the diol component being 100 mol %. In one embodiment, the diol component of a polyester composition useful in the present disclosure may comprise 0 to less than 10 mol % of 1,4-cyclohexanedimethanol, based on the total mole % of the diol component being 100 mol %. In one embodiment, the diol component of the polyester compositions useful in the present disclosure may comprise 0.01 to 5 mole percent of 1,4-cyclohexanedimethanol, based on the total mole percent of the diol component being 100 mole percent. In one embodiment, the diol component of the polyester compositions useful in the present disclosure may comprise 0 to less than 5 mole percent of 1,4-cyclohexanedimethanol, based on the total mole percent of the diol component being 100 mole percent.

[0062]

[0066] Of course, some other diol residues may be generated in situ during processing. In one embodiment, the diol component of the polyester compositions described herein may include diethylene glycol residues generated in situ during processing, or may be intentionally added, or may be both in any amount. For example, in one embodiment, a polyester composition useful in the present disclosure may include 1 to 15 mol%, or 2 to 12 mol%, or 2 to 11 mol%, or 2 to 10 mol%, or 2 to 9 mol%, or 3 to 12 mol%, or 3 to 11 mol%, or 3 to 10 mol%, or 3 to 9 mol%, or 4 to 12 mol%, or 4 to 11 mol%, or 4 to 10 mol%, or 4 to 9 mol%, or 5 to 12 mol%, or 5 to 11 mol%, or 5 to 10 mol%, or 5 to 9 mol% of diethylene glycol residues, based on the total mol% of the diol component being 100 mol%.

[0063]

[0067] In one embodiment, the total amount of diethylene glycol residues present in the polyester compositions useful in the present disclosure, whether formed in situ during processing, intentionally added, or both, based on the total mole percent of the diol components being 100 mole percent, can be 4 mole percent or less, or 3.5 mole percent or less, or 3.0 mole percent or less, or 2.5 mole percent or less, or 2.0 mole percent or less, or 1.5 mole percent or less, or 1.0 mole percent or less, or from 1 to 4 mole percent, or from 1 to 3 mole percent, or from 1 to 2 mole percent, or from 2 to 8 mole percent, or from 2 to 7 mole percent, or from 2 to 6 mole percent, or from 2 to 5 mole percent, or from 3 to 8 mole percent, or from 3 to 7 mole percent, or from 3 to 6 mole percent, or from 3 to 5 mole percent, or in some embodiments, no intentionally added diethylene glycol residues, based on the total mole percent of the diol components being 100 mole percent.

[0064]

[0068] In all embodiments, the remainder of the diol component may comprise any amount of ethylene glycol residues, based on the total mole percent of the diol component being 100 mole percent. In one embodiment, the polyester portion of the polyester composition useful in the present disclosure may be 50 mole percent or more, or 55 mole percent or more, or 60 mole percent or more, or 65 mole percent or more, or 70 mole percent or more, or 75 mole percent or more, or 80 mole percent or more, or 85 mole percent or more, or 90 mole percent or more, or 95 mole percent or more, or 50-85 mole percent, or 50-80 mole percent, or 55-80 mole percent, or 60-80 mole percent, or 50-75 mole percent, or 55-75 mole percent, or 60-75 mole percent, or 65-75 mole percent, or 70-80 mole percent, or 75-85 mole percent ethylene glycol residues, based on the total mole percent of the diol component being 100 mole percent.

[0065]

[0069] In one embodiment, the diol component of the polyester compositions useful in the present disclosure may comprise up to 20 mol%, or up to 19 mol%, or up to 18 mol%, or up to 17 mol%, or up to 16 mol%, or up to 15 mol%, or up to 14 mol%, or up to 13 mol%, or up to 12 mol%, or up to 11 mol%, or up to 10 mol%, or up to 9 mol%, or up to 8 mol%, or up to 7 mol%, or up to 6 mol%, or up to 5 mol%, or up to 4 mol%, or up to 3 mol%, or up to 2 mol%, or up to 1 mol% of one or more modified diols (a modified diol is defined as a diol that is not ethylene glycol, diethylene glycol, neopentyl glycol, or 1,4-cyclohexanedimethanol). In certain embodiments, the polyester compositions useful in the present disclosure may comprise up to 10 mol% of one or more modified diols. In certain embodiments, the polyesters useful in the present disclosure may comprise up to 5 mol% of one or more modified diols. In certain embodiments, polyesters useful in the present disclosure may contain 3 mole percent or less of one or more modified diols. In other embodiments, polyesters useful in the present disclosure may contain 0 mole percent of one or more modified diols. However, some other diol residues may be formed in situ, and the resulting amount of residues formed in situ is also considered an embodiment of the present disclosure.

[0066]

[0070] In some embodiments, the modifying diols used in the polyesters, as defined herein, when used, contain 2 to 16 carbon atoms. Examples of modifying diols include, but are not limited to, 1,2-propanediol, 1,3-propanediol, isosorbide, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, p-xylene glycol, polytetramethylene glycol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), and mixtures thereof. In one embodiment, isosorbide is the modifying diol. In another embodiment, the modifying diol includes, but is not limited to, at least one of 1,3-propanediol and 1,4-butanediol. In one embodiment, 1,3-propanediol and / or 1,4-butanediol may be excluded. When 1,4- or 1,3-butanediol is used, it may provide, in one embodiment, 4 mol% or more, or 5 mol% or more. In one embodiment, the at least one modifying diol is 1,4-butanediol present in an amount of 5 to 25 mole %. In certain embodiments, the polyester composition does not include any added modifying diol.

[0067]

[0071] In one embodiment, a crystallizable polyester composition is provided in which 1,4-cyclohexanedimethanol residues are present in an amount of 0.01 to about 10 mole %, diethylene glycol residues are present in an amount of 2 to 9 mole %, neopentyl glycol residues are present in an amount of 5 to 30 mole %, and ethylene glycol residues are present in an amount of 60 mole % or greater, based on the total mole % of the diol component being 100 mole %.

[0068]

[0072] In one embodiment, the polyester compositions useful in the present disclosure may include at least one chain extender. Suitable chain extenders include, but are not limited to, polyfunctional isocyanates (including, but not limited to, difunctional), polyfunctional epoxides, including, for example, epoxidized novolacs, and phenoxy resins. In certain embodiments, the chain extender may be added at the end of the polymerization process or after the polymerization process. If added after the polymerization process, the chain extender may be incorporated by compounding or addition during a conversion process, such as injection molding or extrusion.

[0069]

[0073] In certain embodiments, the amount of chain extender used may vary depending on the particular monomer composition used and the physical properties desired, but is generally from about 0.1% to about 10% by weight, e.g., from about 0.1% to about 5% by weight, based on the total weight of the polyester.

[0070]

[0074] It is contemplated that the polyester compositions useful in this disclosure may possess at least one of the intrinsic viscosity ranges described herein and at least one of the monomer ranges for the polyester compositions described herein, unless otherwise indicated. It is further contemplated that the polyester compositions useful in this disclosure may possess at least one of the Tg ranges described herein and at least one of the monomer ranges for the polyester compositions described herein, unless otherwise indicated. It is further contemplated that the polyester compositions useful in this disclosure may possess at least one of the intrinsic viscosity ranges described herein, at least one of the Tg ranges described herein, and at least one of the monomer ranges for the polyester compositions described herein, unless otherwise indicated.

[0071]

[0075] In embodiments of the present disclosure, the polyester compositions useful in the present disclosure may exhibit at least one of an intrinsic viscosity of 0.50-1.2 dL / g, 0.50-1.0 dL / g, 0.50-0.90 dL / g, 0.50-0.80 dL / g, 0.55-0.80 dL / g, 0.60-0.80 dL / g, 0.65-0.80 dL / g, 0.70-0.80 dL / g, 0.50-0.75 dL / g, 0.55-0.75 dL / g, or 0.60-0.75 dL / g, measured in 60 / 40 (wt / wt) phenol / tetrachloroethane at 25° C. and a concentration of 0.5 g / dL.

[0072]

[0076] In one embodiment, the glass transition temperature and strain-induced crystalline melting point (Tg and Tm, respectively) of a polyester are measured using a Thermal Analyst Instrument TA DSC 2920 at a scan rate of 20°C / min. Tm was measured during the first heating step of the stretched sample, and Tg was measured during the second heating step. In yet another embodiment, samples were crystallized in a forced air oven at 165°C for 30 minutes or 170°C for 2 hours before analysis by DSC. For all samples, the crystalline melting point is typically absent during the second heat of the DSC scan at a heating rate of 20°C / min.

[0073]

[0077] In certain embodiments, the oriented films, shrink films, and thermoformed sheets of the present disclosure comprise a crystallizable polyester / polyester composition in which the polyester has a Tg of 60-80° C., 70-80° C., 65-80° C., 74-77° C., 72-77° C., or 65-75° C. In certain embodiments, the polyester has an intrinsic viscosity of 0.68-0.75 dL / g when measured in 60 / 40 (wt / wt) phenol / tetrachloroethane at 25° C. and a concentration of 0.5 g / dL, and the polyester has a Tg of 72-77° C. when measured using a Thermal Analyst Instrument TA DSC 2920 at a scan rate of 20° C. / min.

[0074]

[0078] In certain embodiments, these Tg ranges can be met with or without at least one plasticizer added during polymerization or extrusion or compounding.

[0079] In one embodiment, certain crystallizable polyester compositions useful in the present disclosure may be visually clear, the term "visually clear" being defined herein as the apparent absence of haze, mist, and / or turbidity upon visual inspection.

[0075]

[0080] In one embodiment, the polyester portion of the crystallizable polyester composition useful in the present disclosure may be produced by processes known in the literature, such as processes in homogeneous solution, transesterification processes in the melt, and two-phase interfacial processes. For methods of producing polyesters, see U.S. Pat. No. 3,772,405, the disclosure of which is incorporated herein by reference.

[0076]

[0081] In certain embodiments, the crystallizable polyester compositions may be prepared by condensing a dicarboxylic acid or dicarboxylic acid ester with a diol in the presence of a catalyst in an inert atmosphere, gradually increasing the temperature during the condensation process, and then conducting the condensation at low pressure during the latter part of the condensation process, which processes are described in more detail in U.S. Pat. No. 2,720,507, which is incorporated herein by reference.

[0077]

[0082] In one aspect, the present disclosure is a catalyst system for preparing polyester compositions. In one aspect, the present disclosure is a catalyst system for preparing polyester compositions comprising neopentyl glycol (NPG or 2,2-dimethyl-1,3-propanediol). In one embodiment, the catalyst system of the present disclosure is suitable for polyesters comprising neopentyl glycol (NPG) and / or 1,4-cyclohexanedimethanol (CHDM). In one embodiment, the catalyst system of the present disclosure is also suitable for use with polyester compositions comprising terephthalic acid, ethylene glycol, diethylene glycol, NPG, and CHDM. In one embodiment, the catalyst system is also suitable for use with polyester compositions that do not contain NPG but do comprise terephthalic acid, ethylene glycol, and 1,4-cyclohexanedimethanol. In one embodiment, process improvements are observed when the titanium concentration is kept very low and the reaction temperature is increased above the temperature range typically used to produce these types of polyester compositions.

[0078]

[0083] In one aspect, the catalyst system of the present disclosure combines low concentrations of titanium and antimony, and the system is active over a wide range of polymerization temperatures, especially at high polymerization temperatures. In one embodiment, phosphorus is optionally used as a catalyst moderator. In certain embodiments, when phosphorus is used, the concentration of the phosphorus compound is determined based on the concentrations of titanium and antimony used in the catalyst system. In one embodiment, the amount of phosphorus compound used is determined based on the final polymerization temperature.

[0079]

[0084] In one embodiment, the catalyst system of the present disclosure comprises a titanium compound at a concentration level of 2 to 15 ppm of titanium based on the weight of the polyester produced. In one embodiment, the catalyst system of the present disclosure comprises a titanium compound at a concentration level of 4 to 12 ppm of titanium based on the weight of the polyester produced. In one embodiment, the catalyst system of the present disclosure comprises a titanium compound at a concentration level of 3 to 10 ppm of titanium based on the weight of the polyester produced. In one embodiment, the catalyst system of the present disclosure comprises a titanium compound at a concentration level of 1 to 20 ppm of titanium based on the weight of the polyester produced. In one embodiment, the catalyst system comprises a titanium compound at a concentration level of 20 ppm or less based on the weight of the polyester produced. In one embodiment, the catalyst system comprises a titanium compound at a concentration level of 15 ppm or less based on the weight of the polyester produced. In one embodiment, the catalyst system comprises a titanium compound at a concentration level of 14 ppm or less based on the weight of the polyester produced. In one embodiment, the catalyst system comprises a titanium compound at a concentration level of 13 ppm or less based on the weight of the polyester produced. In one embodiment, the catalyst system contains a titanium compound at a concentration level of 12 ppm or less of titanium based on the weight of the polyester produced. In one embodiment, the catalyst system contains a titanium compound at a concentration level of 10 ppm or less of titanium based on the weight of the polyester produced. In one embodiment, the catalyst system contains a titanium compound at a concentration level of 7 ppm or less of titanium based on the weight of the polyester produced. In one embodiment, the catalyst system contains a titanium compound at a concentration level of 5 ppm or less of titanium based on the weight of the polyester produced. In one embodiment, the titanium compound is a titanate tetraalkyl ester, such as tetraisopropyl titanate. In one embodiment, the titanium compound is selected from titanium tetraalkoxides, such as titanium tetraisopropoxide, titanium tetraethoxide, or titanium tetrabutoxide, or titanate tetraalkyl esters, such as tetraisopropyl titanate, and mixtures thereof.

[0080]

[0085] In one embodiment, the catalyst system comprises an antimony compound at a concentration level of 50 to 150 ppm of antimony based on the weight of the polyester produced. In one embodiment, the catalyst system comprises an antimony compound at a concentration level of 70 to 140 ppm of antimony based on the weight of the polyester produced. In one embodiment, the catalyst system comprises an antimony compound at a concentration level of 90 to 130 ppm of antimony based on the weight of the polyester produced. In one embodiment, the catalyst system comprises an antimony compound at a concentration level of 100 to 120 ppm of antimony based on the weight of the polyester produced. In one embodiment, the antimony compound is antimony trioxide. In one embodiment, the antimony compound is antimony trioxide, antimony acetate, or antimony oxalate. In one embodiment, the antimony compound of the catalyst system is dissolved in one of the glycols used in the polyester composition.

[0081]

[0086] In one embodiment, the phosphorus concentration level is 0 to 90 ppm based on the weight of the polyester produced. In one embodiment, the phosphorus concentration level is 0 to 50 ppm based on the weight of the polyester produced. In one embodiment, the phosphorus concentration level is 2 to 75 ppm based on the weight of the polyester produced. In one embodiment, the phosphorus concentration level is 2 to 50 ppm based on the weight of the polyester produced. In one embodiment, the phosphorus concentration level is 10 to 60 ppm based on the weight of the polyester produced. In one embodiment, the antimony compound concentration level depends on the temperature in the final reaction stage or finishing zone. In one embodiment, the antimony compound concentration level depends on the concentration of titanium used. In one embodiment, the antimony compound concentration level depends on the temperature of the final reaction stage as well as the concentration of titanium used.

[0082]

[0087] In one aspect of the present disclosure, the polymerization temperature is much higher than that of a standard copolyester formation reaction. In one embodiment, the polymerization temperature is 275°C to 310°C. In one embodiment, the polymerization temperature is 285°C to 300°C. In one embodiment, the polymerization temperature is 290°C to 300°C.

[0083]

[0088] In one embodiment, to produce a high IV (intrinsic viscosity) polyester with excellent color, the polymerization temperature is 290°C, the titanium concentration is 8 ppm or less with an antimony loading of 125 ppm and a phosphorus loading of 0-8 ppm. In one embodiment, to produce a high IV polyester with excellent color, the polymerization temperature is 300°C, the titanium concentration is 13 ppm or less with an antimony loading of 100 ppm and a phosphorus loading of 59-60 ppm.

[0084]

[0089] In one embodiment, both the catalyst components and the phosphorus source are added subsequent to the esterification of terephthalic acid. In one embodiment, the conversion of terephthalic acid groups to their ester form by one or more of the glycols used is 90%. In one embodiment, higher conversions of available carboxylic acid ends, up to 100%, can be achieved with the catalyst system of the present disclosure. In one embodiment, the catalyst components may be added together, or they may be added separately. In another embodiment, the phosphorus is added as a separate feed subsequent to the addition of the catalyst.

[0085]

[0090] In one embodiment, no changes to the reaction procedures typically used in high titanium-phosphorus systems are required, other than the option to utilize higher finishing (polymerization) temperatures.

[0091] This catalyst system allows users to prepare NPG-containing polyesters with superior production rates and product color compared to titanium-only systems. The ability to use high reaction temperatures without adversely affecting color allows temperature to be used as a production rate-altering variable. This option is not typically available with traditional titanium catalyst systems, as they are sensitive to elevated temperatures.

[0086]

[0092] In one aspect, the polyester compositions of the present disclosure may be produced using any polycondensation reaction conditions known in the art. They may be produced by continuous, semi-continuous, and batch modes of operation and may utilize a variety of reactor types. Examples of suitable reactor types include, but are not limited to, stirred tank, continuous stirred tank, slurry, tubular, wiped-film, falling film, or extrusion reactors.

[0087]

[0093] The term "continuous" as used herein means a process in which reactants are introduced and products are removed simultaneously in an uninterrupted manner. This process is conveniently run as a continuous process for economic reasons and to produce light-colored polymers, since residence in the reactor at high temperatures for too long a period of time can cause the polyester to deteriorate in appearance.

[0088]

[0094] The polyesters of the present disclosure can be prepared by any procedure known to those skilled in the art. The reaction of the diol component and the dicarboxylic acid component can be carried out using conventional polyester polymerization conditions. For example, when preparing the polyester from the ester form of the dicarboxylic acid component by transesterification, the reaction process can include at least two steps.

[0089]

[0095] In one embodiment of the present disclosure, polyesters are produced in two major stages. The first stage involves reacting starting materials to produce monomers and / or oligomers. If the starting materials entering the first stage contain acid end groups, such as TPA or isophthalic acid, this first stage is called esterification. In the second stage, the monomers and / or oligomers are further reacted to produce the final polyester product. This second stage is commonly called the polycondensation stage. The polycondensation stage can be a single step or can be divided into a pre-polycondensation (or prepolymerization) step and a final (or finishing) polycondensation step.

[0090]

[0096] In the first stage, the esterification step, a diol component, such as ethylene glycol, is reacted with a dicarboxylic acid component, such as terephthalic acid, at a temperature of about 150°C to about 270°C for about 0.5 to about 8 hours at a pressure ranging from about 5 to 60 pounds per square inch ("psig" or "psi"). In one embodiment, the esterification or transesterification reaction temperature is about 180°C to about 230°C for about 1 hour to about 4 hours, and the pressure ranges from about 103 kPa (15 psig) to about 276 kPa (40 psig). In one embodiment, the esterification or transesterification reaction temperature is about 240°C to about 270°C for about 1 hour to about 4 hours, and the pressure ranges from about 5 psig to about 50 psig. The reaction product is then heated at a higher temperature and under reduced pressure to produce a polyester by eliminating the diol, which is readily volatilized and removed from the system under these conditions.

[0091]

[0097] The second stage, the prepolymerization or polycondensation step, is generally continued under higher vacuum conditions for about 0.1 to about 6 hours, or about 0.2 to about 2 hours, at a temperature ranging from about 250°C to about 275°C, or from about 255°C to about 270°C, or from about 260°C to about 270°C, until a polymer having the desired degree of polymerization, as measured by intrinsic viscosity, is obtained. The polycondensation step may be carried out under reduced pressure ranging from about 200 mmHg to about 500 mmHg. In one embodiment, the temperature of the prepolymerization or polycondensation reaction ranges from about 240°C to about 270°C for about 1 hour to about 4 hours, and the pressure ranges from about 200 mmHg to about 500 mmHg. Stirring or other suitable means or conditions are used in both stages to ensure sufficient heat transfer and surface regeneration of the reaction mixture.

[0092]

[0098] In certain embodiments, the reaction rates of both stages, esterification and polycondensation, may be increased by the presence of a catalyst. In one embodiment, the catalyst is added to the esterification reaction. In one embodiment, the catalyst is added to the polycondensation reaction. In one embodiment, the titanium compound and antimony compound are added together, and the phosphorus compound is added as a separate feed following the addition of the catalyst. In one embodiment, the titanium compound, antimony compound, and phosphorus compound are added following the esterification of terephthalic acid.

[0093]

[0099] In one embodiment, there is a finishing or final polycondensation step, in which the reaction is continued until the desired IV is reached. In one aspect of the disclosure, this final finishing step is carried out at a higher temperature (compared to titanium-only catalyst systems). In one embodiment, useful finishing temperatures range from 280 to 310°C, or 285 to 300°C. Higher finishing temperatures allow for the production of high IV polyesters with excellent color.

[0094]

[0100] One embodiment of the present disclosure is a process for finishing a polycondensate to produce a polyester, wherein the polyester has an intrinsic viscosity of at least 0.50 g / dL or 0.50-0.90 g / dL, and the polymerization temperature during finishing is increased to 280-320°C and the pressure is 0.3-7 mmHg.

[0095]

[0101] For example, one embodiment of the present disclosure is a process for preparing a crystallizable reactor-grade polyester composition, the process comprising reacting a diacid component comprising terephthalic acid residues with a diol component comprising neopentyl glycol residues, 1,4-cyclohexanedimethanol residues, diethylene glycol residues, and ethylene glycol residues in the presence of 2 to 15 ppm of a titanium compound and 50 to 150 ppm of an antimony compound at an esterification reaction temperature of 240 to 270° C. and a pressure of 5 to 50 psi to form an ester. a step of prepolymerizing the esterified product in the presence of 0 to 90 ppm of a phosphorus compound at a prepolymerization temperature of 255 to 275°C and a pressure of 200 to 500 mmHg to produce a polycondensation product; and a step of finishing the polycondensation product to produce a polyester, wherein the intrinsic viscosity of the polyester is at least 0.50 g / dL or 0.50 to 0.90 g / dL, and the polymerization temperature during the finishing treatment is increased to 280 to 320°C and the pressure is 0.3 to 7 mmHg.

[0096]

[0102] Another embodiment is a process for preparing a crystallizable reactor-grade polyester composition, comprising the steps of: reacting a diacid component comprising terephthalic acid residues with a diol component comprising neopentyl glycol residues, 1,4-cyclohexanedimethanol residues, diethylene glycol residues, and ethylene glycol residues at an esterification reaction temperature of 240-270°C and a pressure of 5-50 psi to produce an esterification product; prepolymerizing the esterification product in the presence of 2-15 ppm of a titanium compound, 50-150 ppm of an antimony compound, and 0-90 ppm of a phosphorus compound at a polycondensation temperature of 255-275°C to produce a pre-polycondensation product; and finishing the polycondensation product to produce a polyester, wherein the polyester has an intrinsic viscosity of at least 0.50 g / dL or 0.50-0.90 g / dL, and the polymerization temperature during the finishing treatment is increased to 280-320°C and the pressure is 0.3-7 mmHg.

[0097]

[0103] To ensure complete reaction of the diol and dicarboxylic acid components via transesterification, an excess of about 1.05 to about 2.5 moles of diol component per mole of dicarboxylic acid component may be desirable, although those skilled in the art will recognize that the ratio of diol component to dicarboxylic acid component is generally determined by the design of the reactor in which the reaction process occurs.

[0098]

[0104] In some embodiments, suitable glycols include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, p-xylene glycol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, polytetramethylene glycol, isosorbide, or mixtures thereof.

[0099]

[0105] In one embodiment, copolyesters suitable for use in the present disclosure are prepared from monomers such as, for example, dimethyl terephthalate (DMT), terephthalic acid (TPA), isophthalic acid (IPA), 1,4-cyclohexanedicarboxylic acid (CHDA), ethylene glycol (EG), diethylene glycol (DEG), neopentyl glycol (NPG), 1,4-cyclohexanedimethanol (CHDM), and 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD).

[0100]

[0106] In accordance with the present disclosure, a process for preparing a polyester article is provided.

[0107] In one embodiment, the reaction zones may be separate vessels, typically continuous stirred tank reactors (CSTRs), which may be integrated units having multiple esterification zones with appropriate dividers and controls. Similarly, the reaction zones may be separate vessels, typically wiped-film or thin-film CSTRs, which may be combined into one or more integrated units having multiple polycondensation zones with appropriate dividers and controls. Various other types of esterification and polycondensation reactors and reactor configurations are known in the art and may be adapted for use in accordance with the present disclosure.

[0101]

[0108] In one embodiment, a paste consisting of EG and TPA in a 2:1 molar ratio is fed to a paste tank. In one embodiment, additional EG is fed to the first reaction zone or reactor 1, and other glycols, such as CHDM, TMCD, NPG, and DEG, are also fed to the first reaction zone at the same location. In one embodiment, these monomers may be added separately and / or directly to the first reaction zone.

[0102]

[0109] In one embodiment, the reaction mixture in the first reaction zone is heated via a recycle loop containing a heat exchanger. Esterification occurs in the first reaction zone to form a first esterification product containing copolyester monomers, oligomers, or both, and unreacted TPA, EG, and other glycols, such as CHDM, TMCD, NPG, or DEG. The reaction product of the first reaction zone is then delivered to a second reaction zone. Further esterification occurs in the second reaction zone to form a second esterification product containing additional polyester monomers, oligomers, or both. In certain embodiments, the average chain length of the monomers and / or oligomers at the end of the esterification stage may be less than 25, between 1 and 20, or between 5 and 15.

[0103]

[0110] In one embodiment, the reaction product of the second reaction zone is then delivered to a third reaction zone to produce a prepolymerized product comprising oligomers of a copolyester. In some embodiments, the third reaction zone converts the monomers from the esterification step to oligomers having an average chain length in the range of 2 to 40, 5 to 35, or 10 to 30.

[0104]

[0111] The prepolymerized product is then delivered to one or more final reaction or finishing zones, where further polycondensation occurs to produce a copolyester having the desired average chain length or IV, which is then withdrawn from the finishing zone for further processing, such as forming into pellets via an extruder connected to an underwater pelletizer.

[0105]

[0112] In one embodiment, the average residence time of the reactants in the reaction step is 2 hours or less, 1.75 hours or less, 1.5 hours or less, 1.25 hours or less, 1 hour or less, or 0.75 hours or less. In various embodiments, the average residence time of the reactants in the reaction step is 30 minutes to 40 minutes.

[0106]

[0113] In one embodiment, the average residence time of the reactants in the esterification step is 2 hours or less, 1.75 hours or less, 1.5 hours or less, 1.25 hours or less, 1 hour or less, or 0.75 hours or less. In various embodiments, the average residence time of the reactants in the esterification step (d) is 30 to 40 minutes.

[0107]

[0114] In various embodiments, the overall molar ratio of EG:TPA introduced into the process ranges from 2.3:1 to 3.0:1.

[0115] In various embodiments, the overall molar ratio of EG:TPA introduced into the process ranges from 2.3:1 to 2.71:1.

[0108]

[0116] The catalysts may be added either during the esterification stage or during the polycondensation stage, hi one embodiment, they are added to the first reaction zone with the feed.

[0117] In some embodiments, phosphorus compounds are often added with catalysts to improve thermal stability. Phosphorus compounds useful as thermal stabilizers include phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphonous acid, and various esters and salts thereof. The esters may be alkyl, branched alkyl, substituted alkyl, difunctional alkyl, alkyl ether, aryl, and substituted aryl. In some embodiments, a suitable thermal stabilizer includes triphenyl phosphate. In one embodiment, phosphorus is added in the range of 0 to 90 ppm based on the weight of the copolymerized polyester.

[0109]

[0118] In various embodiments, one or more other additives may be added to the starting materials, copolyesters, and / or copolyester monomers / oligomers at one or more locations within the process. In various embodiments, suitable additives may include, for example, trifunctional or tetrafunctional comonomers such as trimellitic anhydride, trimethylolpropane, pyromellitic dianhydride, pentaerythritol, or other polyacids or polyols; crosslinking or other branching agents; colorants; toners; pigments; carbon black; glass fibers; fillers; impact modifiers; antioxidants; ultraviolet absorbing compounds; oxygen scavenging compounds; and the like.

[0110]

[0119] Processes according to the present disclosure are particularly suitable for use on an industrial scale, for example, they may be carried out on commercial production lines capable of flowing polymer at rates of 500 to 30,000 pounds per hour.

[0111]

[0120] In another aspect, the present disclosure relates to copolyesters produced from the processes of the present disclosure.

[0121] In some embodiments, during the process of making the polyesters useful in the present disclosure, certain agents that color the polymer, including toners or dyes, may be added to the melt. In one embodiment, the resulting polyester polymer melt phase product b *To reduce the value, blue toners are added to the melt. Such blueing agents include blue inorganic and organic toners and / or dyes. Additionally, red toners and / or dyes are used to reduce the a * The color values ​​may be adjusted. Organic toners may be used, such as the blue and red organic toners described in U.S. Patent Nos. 5,372,864 and 5,384,377, which are incorporated herein by reference in their entireties. The organic toner may be supplied as a premix composition. The premix composition may be a neat blend of red and blue compounds, or the composition may be pre-dissolved or slurried in one of the polyester raw materials, such as ethylene glycol.

[0112]

[0122] The total amount of toner components added may depend on the amount of inherent yellow color in the substrate polyester and the efficacy of the toner. In one embodiment, the combined organic toner components may be used at a maximum concentration of about 15 ppm and a minimum concentration of about 0.5 ppm. In one embodiment, the total amount of blue additive may range from 0.5 to 10 ppm. In one embodiment, the toner may be added to the esterification zone or polycondensation zone. Preferably, the toner is added to the esterification zone or an early stage of the polycondensation zone, such as a prepolymerization reactor.

[0113]

[0123] In embodiments, the polyester composition may contain, at 0.01 to 25 weight percent of the total composition, common additives such as mold release agents, anti-slip agents, antiblocking agents, flame retardants, plasticizers, glass bubbles, nucleating agents, stabilizers including, but not limited to, UV stabilizers and thermal stabilizers, and / or their reaction products, fillers, and impact modifiers. Examples of commercially available impact modifiers include, but are not limited to, ethylene / propylene terpolymers, functionalized polyolefins such as methyl acrylate and / or glycidyl methacrylate, styrenic block copolymer impact modifiers, and various acrylic core / shell impact modifiers. Residues of such additives are also considered part of the polyester composition.

[0114]

[0124] In one embodiment, the crystallizable composition of the present disclosure is used to produce films and sheets, including heat-shrinkable films and thermoformable sheets. Heat-shrinkable plastic films are used as coverings to hold objects together and as exterior materials for bottles, cans, and other types of containers. For example, such films are used to cover the lid, neck, shoulder, body, or entire bottle for labeling, protection, packaging, or to enhance product value, and for other reasons. Furthermore, such films may be used as coverings to group and package objects such as boxes, bottles, plates, sticks, notebooks, etc., and such films may also be tightly sealed as packaging. These uses utilize the film's shrinkability and internal shrinkage stress.

[0115]

[0125] Historically, polyvinyl chloride (PVC) film dominated the shrink film market. However, polyester film has become an important alternative because it does not suffer from the environmental issues associated with PVC film. Polyester shrink film ideally possesses properties very similar to those of PVC film, allowing it to function as a "drop-in" replacement and be processed in existing heat shrink tunnel equipment. Desired PVC film properties for replacement include: (1) a relatively low shrink initiation temperature; (2) a total shrink rate that increases gradually and in a controlled manner with increasing temperature; (3) a low shrink force to prevent collapse of the underlying container; (4) a high total shrink rate (e.g., greater than 50%); and (5) inherent film toughness to prevent unwanted tearing and splitting of the film before and after shrinking.

[0116]

[0126] To be viable for this application, heat-shrinkable films must meet various standards. The film must be strong, shrink in a controlled manner, and provide sufficient shrinkage force to hold itself against the bottle surface without crushing the contents. Furthermore, when these labels are applied to polyester containers, they must not interfere with the recycling process of PET bottles. In fact, it would be advantageous if the label were also recyclable, allowing the entire bottle to be recycled and converted into a new product without creating additional handling requirements or new environmental problems. Heat-shrinkable films are manufactured from a variety of raw materials to meet a range of material needs. This disclosure describes unique and unexpected effects achieved by combining polyester shrink film labels with specific monomers to improve their recyclability.

[0117]

[0127] Polyester shrink film compositions are commercially used as shrink film labels for food, beverages, personal care products, and household goods. These shrink films are often combined with clear polyethylene terephthalate (PET) bottles or containers. The entire product (bottle and label) is then sent for recycling. At typical recycling sites, PET and shrink film materials are often mixed together at the end of the process due to their similar compositions and densities. Drying the PET flakes is necessary to remove residual water that adheres to the PET during the recycling process. During the recycling process, PET is typically dried at temperatures exceeding 200°C. At these temperatures, typical polyester shrink film resins soften and become sticky, often forming agglomerates with the PET flakes. These agglomerates must be removed before further processing. These agglomerates reduce the yield of PET flakes from the process and require additional handling steps.

[0118]

[0128] In embodiments of the present disclosure, a particular oriented film and / or shrink film comprising a polyester and / or polyester composition useful in the present disclosure can have any unique combination of the following properties: excellent stretchability, controlled shrink properties, particular toughness, particular intrinsic viscosity, particular glass transition temperature (Tg), particular strain-induced crystalline melting point, particular flexural modulus, particular density, particular tensile modulus, particular surface tension, excellent melt viscosity, excellent clarity, and excellent color.

[0119]

[0129] In one embodiment, films and shrink films according to the present disclosure may contain 0.01 to 10 weight percent polyester plasticizer, such as those described in U.S. Patent No. 10,329,393, incorporated herein by reference. In one embodiment, shrink films may contain 0.1 to 5 weight percent polyester plasticizer.

[0120]

[0130] In one aspect, the present disclosure relates to shrink films, extruded sheets, thermoformed articles, and molded articles comprising the crystallizable polyester compositions of the present disclosure. Methods for forming polyester compositions into films and / or sheets are well known in the art. Examples of useful sheets of the present disclosure include, but are not limited to, extruded sheets, compression molded films, calendered films and / or sheets, and solution-cast films and / or sheets. In one aspect, methods for producing films and / or sheets useful for producing shrink films of the present disclosure include, but are not limited to, extrusion, compression molding, calendering, and solution casting.

[0121]

[0131] In one embodiment, the polyester compositions useful in the present disclosure are made into films using any method known in the art for making films from polyesters, such as solution casting, extrusion, compression molding, or calendering. See, for example, U.S. Patent Nos. 6,846,440; 6,551,699; 6,551,688; and 6,068,910, which are incorporated herein by reference.

[0122]

[0132] In one embodiment, the as-formed film is subsequently oriented in one or more directions (e.g., as a uniaxially and / or biaxially oriented film). This orientation of the film can be carried out by any method known in the art using standard orientation conditions. In one embodiment, oriented films of the present disclosure may be produced from films having a thickness of about 100 to 400 μm, such as extruded, cast, or calendered films, and the oriented films may be oriented at temperatures between Tg and Tg+55°C, or between 70°C and 125°C, at a ratio of 5:1 to 3:1, e.g., at temperatures between 70°C and 100°C, at a ratio of 5:1 or 3:1, and the films may be oriented to a thickness of 20 to 80 μm. In one embodiment, orientation of the initial pre-shrunk film may be carried out in a tenter frame according to these orientation conditions. Shrink films of the present disclosure may be produced from oriented films of the present disclosure.

[0123]

[0133] In one embodiment, a shrink film of the present disclosure may have a shrink initiation temperature of from about 55 to about 80° C., or from about 55 to about 75° C., or from about 55 to about 70° C. The shrink initiation temperature is the temperature at which the initiation of shrinkage occurs.

[0124]

[0134] In certain embodiments, polyester compositions useful in the present disclosure may have a density of 1.6 g / cc or less, or 1.5 g / cc or less, or 1.4 g / cc or less, or from 1.1 g / cc to 1.5 g / cc, or from 1.2 g / cc to 1.4 g / cc, or from 1.2 g / cc to 1.35 g / cc.

[0125]

[0135] In one embodiment, many small voids or holes are introduced into a film or molded article to reduce the film's density. This process is called "voiding," sometimes referred to as "cavitating" or "microvoiding." These voids are created by incorporating about 1 to about 50% by weight of small organic or inorganic (including glass microspheres) particles or "inclusions" (known in the art as "void-forming" or "cavitating" agents) into a matrix polymer and then stretching the polymer in at least one direction to orient it. During stretching, small cavities or voids are formed around the void-forming agents. When voids are introduced into a polymer film, the resulting voided film is not only less dense than a non-voided film, but also more opaque and exhibits a paper-like surface. This surface also has the advantage of improving printability; the surface can accept more ink at a substantially greater volume than a non-voided film. Typical examples of apertured films are U.S. Patent Nos. 3,426,754; 3,944,699; 4,138,459; 4,582,752; 4,632,869; 4,770,931; 5,176,954; 5,435,955; 5,843,578; 6,004,664; 6,287,68 0; 6,500,533; 6,720,085; U.S. Patent Application Publication Nos. 2001 / 0036545; 2003 / 0068453; 2003 / 0165671; 2003 / 0170427; Japanese Patent Application Publication Nos. 61-037827; 63-193822; 2004-181863; European Patent Application Publication No. 0 581 970 B1; and European Patent Application Publication No. 0 214 859 A2.

[0126]

[0136] In certain embodiments, the as-extruded film is oriented during stretching. The oriented or shrinkable films of the present disclosure can be made from films of any thickness depending on the desired end use. In one embodiment, a desirable condition is that the oriented and / or shrinkable film can be printed with ink for applications such as labels, photographic films that can be adhered to substrates such as paper, and / or other applications where the films are useful for bottles or containers and can be shrunk to surround the outside. It may be desirable to coextrude the polyesters useful in the present disclosure with another polymer, such as PET, to enable the film to be used as the oriented and / or shrinkable films of the present disclosure. One advantage of the latter coextrusion technique is that, in some embodiments, a tie layer may not be required.

[0127]

[0137] In certain embodiments, the shrink films of the present disclosure shrink slowly with little or no wrinkling. In certain embodiments, the shrink films of the present disclosure have a shrinkage rate in the transverse direction of 40% or less per 5° C. increase in temperature.

[0128]

[0138] In certain embodiments of the present disclosure, shrink films of the present disclosure have a machine direction shrinkage of 10% or less, or 5% or less, or 3% or less, or 2% or less, or no shrinkage, when immersed in water at 65°C for 10 seconds. In certain embodiments of the present disclosure, shrink films of the present disclosure have a machine direction shrinkage of -10% to 10%, -5% to 5%, or -5% to 3%, or -5% to 2%, or -4% to 4%, or -3% to 4%, or -2% to 4%, or -2% to 2.5%, or -2% to 2%, or 0 to 2%, or no shrinkage, when immersed in water at 65°C for 10 seconds. A negative machine direction shrinkage indicates expansion in the machine direction. A positive machine direction shrinkage indicates shrinkage in the machine direction.

[0129]

[0139] In certain embodiments of the present disclosure, the shrink films of the present disclosure have a shrink percentage in the main shrink direction of 50% or more, or 60% or more, or 70% or more when immersed in water at 95°C for 10 seconds.

[0130]

[0140] In certain embodiments of the present disclosure, the shrink film of the present disclosure has a shrinkage percentage of 50 to 90% in the main shrink direction and a shrinkage percentage of 10% or less, or -10% to 10%, in the machine direction when immersed in water at 95°C for 10 seconds.

[0131]

[0141] In one embodiment, polyesters useful in the present disclosure are formed into a film using any method known in the art for producing films from polyesters, such as solution casting, extrusion, compression molding, or calendering. The as-extruded (or as-formed) film is then oriented in one or more directions (e.g., uniaxially and / or biaxially oriented film). This orientation of the film may be carried out by any method known in the art using standard orientation conditions. For example, a uniaxially oriented film of the present disclosure may be made from a film, e.g., an extruded, cast, or calendered film, having a thickness of about 100 to 400 μm, which may be stretched at a ratio of 6.5:1 to 3:1 at a temperature between the Tg of the film and Tg+55°C and stretched to a thickness of 20 to 80 μm. In one embodiment, orientation of the initial as-extruded film may be carried out in a tenter frame according to these orientation conditions.

[0132]

[0142] In certain embodiments of the present disclosure, the shrink films of the present disclosure may have a shrink initiation temperature of from about 55 to about 80° C., or from about 55 to about 75° C., or from about 55 to about 70° C. The shrink initiation temperature is the temperature at which the initiation of shrinkage occurs or the shrinkable film begins to shrink.

[0133]

[0143] In certain embodiments of the present disclosure, the shrink films of the present disclosure may have a shrink initiation temperature of 55°C to 70°C.

[0144] In certain embodiments of the present disclosure, the shrink films of the present disclosure may have a breaking strain of greater than 200% at a stretch rate of 500 mm / min in the direction perpendicular to the main shrink direction according to ASTM method D882.

[0134]

[0145] In certain embodiments of the present disclosure, the shrink films of the present disclosure may have a breaking strain of greater than 300% at a stretch rate of 500 mm / min in the direction perpendicular to the main shrink direction according to ASTM method D882.

[0135]

[0146] In certain embodiments of the present disclosure, the shrink films of the present disclosure may have a tensile stress at break (stress at break) of 20 to 400 MPa, or 40 to 260 MPa, or 42 to 260 MPa, measured according to ASTM method D882.

[0136]

[0147] In certain embodiments of the present disclosure, the shrink films of the present disclosure may have a shrink force of 4 to 18 MPa, or 4 to 15 MPa, as measured by ISO Method 14616, depending on the stretching conditions and desired end use. For example, certain labels made for plastic bottles may have a shrink force of 4 to 8 MPa, and certain labels made for glass bottles may have a shrink force of 10 to 14 MPa, as measured by ISO Method 14616 using a LabThink FST-02 Heat Shrinkage Tester and reported in units of MPa.

[0137]

[0148] In one embodiment of the present disclosure, the polyester composition may be produced by reacting monomers by known methods for producing polyesters, typically referred to as reactor grade compositions.

[0138]

[0149] Molded articles comprised of shrink film, or that do not consist of shrink film but include the film, can also be made from any of the polyester compositions disclosed herein and are included within the scope of the present disclosure.

[0139]

[0150] In one embodiment, when having a pre-oriented thickness of about 100 to 400 μm and subsequently oriented on a tenter frame at a temperature of Tg to Tg+55° C. and a ratio of 6.5:1 to 3:1 to a thickness of about 20 to about 80 μm, the shrink film of the present disclosure exhibits the following properties: (1) upon immersion in 95° C. water for 10 seconds, it shrinks by an amount greater than 60% (or greater than 70%) in the primary shrinkage direction, i.e., in the transverse direction, and by 10% or less (or -5% to 4%) in the machine direction. (2) a shrink onset temperature of about 55°C to about 70°C; (3) a strain at break of greater than 200%, or 200-600%, or 200-500%, or 226-449%, or 250-455%, in accordance with ASTM Method D882, at a stretching rate of 500 mm / min in the transverse direction, machine direction, or both; (4) a shrinkage of 40% or less per 5°C temperature increase; and / or (5) a melting point of strain-induced crystallinity of 200°C or greater. Any combination of these properties, or all of these properties, may be present in a shrink film of the present disclosure. A shrink film of the present disclosure may have a combination of two or more of the above-mentioned shrink film properties. A shrink film of the present disclosure may have a combination of three or more of the above-mentioned shrink film properties. A shrink film of the present disclosure may have a combination of four or more of the above-mentioned shrink film properties. In certain embodiments, properties (1) and (2) are present. In certain embodiments, characteristics (1) to (5) are present. In certain embodiments, characteristics (1) to (3), etc. are present.

[0140]

[0151] The shrink percentages herein are based on initial, as-produced films having a thickness of about 20-80 μm that have been tenter-oriented at a ratio of 6.5:1 to 3:1 at temperatures between Tg and Tg+55° C., e.g., a ratio of 5:1 at temperatures between 70° C. and 85° C. In one embodiment, the shrink properties of oriented films used to make the shrink films of the present disclosure were unchanged when the films were heat-treated at temperatures higher than the temperatures at which they were oriented.

[0141]

[0152] The shape of a film useful for making the oriented or shrink films of the present disclosure is not limited in any way. For example, the shape can be a flat film or a film formed into a tube. A film formed into a tube can have its edges bonded or held together during shrinkage using a stitching solvent or adhesive. To produce a shrink film useful in the present disclosure, the polyester is first formed into a flat film and then "uniaxially stretched," meaning that the polyester film is oriented in one direction, and then the edges of the stretched film are bonded using a stitching solvent or adhesive to form a tube or sleeve. The film can also be "biaxially oriented," meaning that the polyester film is oriented in two different directions; for example, the film is stretched in both the machine direction and a direction different from the machine direction. Typically, the two directions are substantially perpendicular, but this is not always the case. For example, in one embodiment, the two directions are the longitudinal direction or machine direction ("MD") of the film (the direction in which the film is produced on the film-making machine) and the transverse direction ("TD") of the film (the direction perpendicular to the MD of the film). Biaxially oriented films may be sequentially oriented, simultaneously oriented, or oriented by some combination of simultaneous and sequential stretching.

[0142]

[0153] Films may be oriented by any conventional method, such as roll stretching, long-gap stretching, tenter stretching, and tubular stretching. Any of these methods may be used to achieve sequential biaxial stretching, simultaneous biaxial stretching, uniaxial stretching, or a combination thereof. The biaxial stretching described above may achieve simultaneous stretching in the machine and transverse directions. Stretching may also be performed first in one direction and then in the other, effectively resulting in biaxial orientation. In one embodiment, film stretching is performed by preheating the film to 5°C to 80°C above its glass transition temperature (Tg). In one embodiment, the film may be preheated to 5°C to 30°C above its Tg. In one embodiment, the stretching rate is 0.5 to 20 inches (1.27 to 50.8 cm) per second. The film may then be oriented, for example, to 2 to 6 times its original dimensions in either the machine direction, the transverse direction, or both. The film may be oriented as a single film layer or may be coextruded with another polyester, such as PET (polyethylene terephthalate), as a multilayer film and then oriented.

[0143]

[0154] In one embodiment, the present disclosure includes an article of manufacture or a molded article comprising a shrink film of any of the shrink film embodiments of the present disclosure. In another embodiment, the present disclosure includes an article of manufacture or a molded article comprising an oriented film of any of the oriented film embodiments of the present disclosure.

[0144]

[0155] In certain embodiments, the present disclosure includes, but is not limited to, shrink films suitable for containers, plastic bottles, glass bottles, packaging, batteries, hot-fill containers, and / or industrial products or other uses. In one embodiment, the present disclosure includes, but is not limited to, oriented films suitable for containers, packaging, plastic bottles, glass bottles, photographic substrates such as paper, batteries, hot-fill containers, and / or industrial products or other uses.

[0145]

[0156] In certain embodiments of the present disclosure, the shrink films of the present disclosure may be formed into labels or sleeves which may then be applied to the wall of a container, an article of manufacture such as a battery, or onto a sheet or film.

[0146]

[0157] The oriented or shrink films of the present disclosure can be applied to molded articles such as tubes or bottles and are commonly used in a variety of packaging applications. For example, films and sheets made from polymers such as polyolefins, polystyrene, polyvinyl chloride, polyester, and polylactic acid (PLA) are frequently used to manufacture shrink labels for plastic beverage or food containers. For example, the shrink films of the present disclosure can be used in many packaging applications, where the shrink films applied to molded articles exhibit properties such as excellent printability, excellent shrink force, excellent texture, high shrink ratio, controlled shrink rate, high stiffness, and recyclability.

[0147]

[0158] The improved shrink properties and recyclability should provide new commercial options such as, but not limited to, shrink films applied to containers, plastic bottles, glass bottles, packaging, batteries, hot fill containers, and / or industrial products or other uses.

[0148]

[0159] In one aspect of the present disclosure, the disclosed polyester compositions are useful as thermoformed and / or thermoformable sheets. The present disclosure is also directed to articles of manufacture incorporating the thermoformed sheets of the present disclosure. In one embodiment, the polyester compositions of the present disclosure are useful as sheets that are easily formed into molded or shaped articles or parts. In one embodiment, the films and / or sheets of the present disclosure can be processed into molded articles or parts by thermoforming. The polyester compositions of the present disclosure may be used in a variety of molding and extrusion applications.

[0149]

[0160] Additionally, in one embodiment, the polyester compositions useful in the thermoformable sheets of the present disclosure may also contain common additives such as colorants, antiblocking agents, slip agents, mold release agents, flame retardants, plasticizers, nucleating agents, stabilizers such as, but not limited to, UV stabilizers, heat stabilizers, fillers, and impact modifiers, in amounts of 0.1 to 25 weight percent of the total composition.

[0150]

[0161] In one embodiment, reinforcing materials may be included in thermoformed sheets comprising the polyester compositions of the present disclosure. For example, suitable reinforcing materials may include carbon fibers, silicates, mica, clay, talc, titanium dioxide, wollastonite, glass flakes, glass beads and fibers, polymeric fibers, and combinations thereof.

[0151]

[0162] In one embodiment, the thermoformed sheet of the present disclosure is a multi-layer sheet, hi one embodiment, at least one layer of the multi-layer sheet is a foam layer, or a foamed polymer or polyester layer.

[0152]

[0163] One aspect of the present disclosure is a method of producing formed or molded parts and articles using thermoforming. Any thermoforming technique or process known to one of ordinary skill in the art can be used to produce the formed or molded articles and parts of the present disclosure.

[0153]

[0164] In one embodiment, the thermoforming process can be carried out in several ways, as taught, for example, in "Technology of Thermoforming" (Throne, James; Hanser Publishers; 1996; pp. 16-29), which is incorporated herein by reference. In some embodiments, the process is a male thermoforming process in which gas or air pressure is applied to a softened sheet, which then stretches and draws the sheet like a bubble, with a male mold placed inside the bubble. A vacuum is then applied to further draw the part and conform it to the surface of the male mold. In this thermoforming process, biaxial stretching / orientation is primarily accomplished in one step as gas or air pressure is applied to the softened sheet. The forming process is then completed by cooling below the Tg of the sheet and using vacuum and a male mold to lock in the orientation in the sheet for a good balance of physical and cosmetic properties. In another embodiment, the process is a female mold thermoforming process in which a vacuum or physical plug is applied to the heat softened sheet to stretch and draw the sheet to approximately the final part dimensions, then internal positive air pressure or an additional external vacuum is applied to draw the sheet and conform it to an external female mold, and the sheet is cooled below the Tg of the sheet to lock in the orientation and form the sheet into an article.

[0154]

[0165] In some embodiments, the bubble formation may be further formed using a plug assist, followed by covering and molding the rising male mold with a sheet, and then applying a vacuum to pull corners, shelf guides, etc. into the mold. In some embodiments, after removal from the mold, the formed part or article may be cut, punched, cornered, etc., as needed.

[0155]

[0166] In another embodiment, thermoforming is a process in which a sheet of the polyester composition of the present disclosure is heated to a temperature sufficient to allow it to deform, and then the heated sheet is forced to conform to the contours of a mold by means such as vacuum assistance, air pressure assistance, and matched mold assistance. In another embodiment, the heated sheet is placed in a mold and forced to conform to the contours of the mold, for example, by applying air pressure, using a vacuum plug assist, or using a matched mold. In some embodiments, thin-walled articles are produced by thermoforming. In some embodiments, thick-walled articles are produced by thermoforming.

[0156]

[0167] In one embodiment, the thermoforming process involves forcing a male mold into a heated sheet, thereby forming the sheet into a desired shape. In certain embodiments, thermoforming involves having the male mold of the article supported between a vacuumed surface or table. In these embodiments, heat from an external heat source, such as a hot air blower, heat lamp, or other radiant heat source, is directed at the sheet. In these embodiments, the sheet is heated to its softening point. In these embodiments, a vacuum is then applied to the table, under the table, and around the mold, drawing the heat-softened sheet toward the table, placing the softened sheet in contact with the mold surface. In these embodiments, the vacuum draws the softened sheet into intimate contact with and conforms to the contours of the mold surface, thereby assuming the shape of the mold. In these embodiments, after the sheet cools, it hardens and the resulting article or part can be removed from the mold.

[0157]

[0168] In one embodiment, the thermoforming process comprises the steps of forming a sheet from the polyester composition of the present disclosure; heating the sheet until it softens and placing the sheet over a mold; drawing the preheated sheet over the heated mold surface; cooling the sheet; and then removing the formed article or part from the mold cavity, or, if desired, heat-setting the formed sheet by maintaining the sheet in contact with the heated mold for a time sufficient to partially crystallize the sheet.

[0158]

[0169] In one embodiment, the thermoforming process comprises the steps of forming a sheet from the polyester composition of the present disclosure; heating the sheet to a temperature at or above the Tg of the polyester; applying gas pressure, vacuum, and / or physical pressure to the heat-softened sheet to stretch the sheet to approximately the final part dimensions; forcing the sheet to conform to the shape of a mold using vacuum or pressure; cooling the sheet to a temperature below the Tg of the polyester; and then removing the thermoformed article or part from the mold.

[0159]

[0170] Sheets used in thermoforming processes may be made by any conventional method known to those skilled in the art. In one embodiment, the sheet is formed by extrusion. In one embodiment, the sheet is formed by calendering. In one embodiment, during the thermoforming process, the sheet is heated to a temperature equal to or greater than the Tg of the polyester. In one embodiment, this temperature is about 10°C to about 60°C higher than the Tg of the polyester. In one embodiment, to achieve shorter forming times, it is necessary to heat the sheet before placing it on the thermoforming mold. In one embodiment, the sheet must be heated above its Tg but below a temperature at which the sheet will flex excessively while being placed over the mold cavity. In one embodiment, the formed sheet may be cooled to a temperature below the Tg of the polyester before being removed from the mold. In one embodiment, the thermoforming method may include vacuum assistance, air assistance, mechanical plug assistance, or a matched mold. In some embodiments, the mold is heated to a temperature equal to or greater than the Tg of the sheet. Selection of the optimal mold temperature depends on the type of thermoforming machine, the configuration and wall thickness of the article being formed, and other factors.

[0160]

[0171] In some embodiments, the heated sheet is stretched by applying and pulling a vacuum.

[0172] In one embodiment, heat setting is a process that thermally induces partial crystallization of a polyester sheet without appreciable orientation. In one embodiment, heat setting is achieved by maintaining contact of the sheet with a heated mold surface for a time sufficient to achieve a level of crystallinity that imparts suitable physical properties to the finished part. In certain embodiments, the level of crystallinity (relative crystallinity) should be greater than 8 cal / g.

[0161]

[0173] In one embodiment, the heat-set part may be removed from the mold cavity by known means for removal. For example, in one embodiment, a blowback is used, which involves introducing compressed air to break the vacuum established between the mold and the formed sheet. In some embodiments, excess material from the formed article or part is then trimmed and the waste material is crushed and recycled.

[0162]

[0174] In some embodiments, the addition of a nucleating agent provides faster crystallization during thermoforming, and therefore faster molding. In one embodiment, a nucleating agent such as a fine particle-sized inorganic or organic material may be used. For example, in one embodiment, suitable nucleating agents include talc, titanium dioxide, calcium carbonate, and immiscible or crosslinked polymers. In one embodiment, the nucleating agent may be used in an amount ranging from about 0.01% to about 20% based on the weight of the article. In one embodiment, other conventional additives, such as pigments, dyes, plasticizers, crack inhibitors, and stabilizers, may be used as needed for thermoforming. In some embodiments, the crack inhibitor improves impact strength, and the nucleating agent provides faster crystallization. In some embodiments, crystallization is necessary to achieve high temperature stability.

[0163]

[0175] In one embodiment, a foamed polyester sheet is prepared by foaming a polyester composition of the present disclosure with a chemical and / or physical foaming agent, extruding the foamed polyester into a sheet, and thermoforming the foamed polyester sheet. Additives to improve the properties of the foamed polyester sheet may be added to the polyester before foaming. Examples of such additives include slip agents, antiblocking agents, plasticizers, optical brighteners, and UV inhibitors. In one embodiment, the foamed polyester sheet may be an extrusion or laminate coated on one or both sides using conventional techniques to improve its properties. In one embodiment, the coating material may be a printed surface that provides product labeling, rather than the foam sheet itself.

[0164]

[0176] In certain embodiments, the compositions of the present disclosure are useful as formed or molded plastic parts or solid plastic articles. In some embodiments, the compositions of the present disclosure are useful as thermoformed parts or articles. In some embodiments, the compositions of the present disclosure are suitable for use in any application where a clear, rigid plastic is required. For example, in some embodiments, the compositions of the present disclosure are suitable for use as parts for disposable knives, forks, spoons, plates, cups, straws, eyeglass frames, toothbrush handles, toys, automotive accessories, tool handles, camera parts, electronic device parts, razor parts, ink pen barrels, disposable syringes, bottles, and the like. In one embodiment, the compositions of the present disclosure are useful as plastics, films, fibers, and sheets.

[0165]

[0177] In one embodiment, the compositions are useful as plastics for manufacturing bottles, bottle caps, eyeglass frames, cutlery, disposable cutlery, cutlery handles, shelves, shelf dividers, electronic device housings, electronic device cases, computer monitors, printers, keyboards, tubing, automotive parts, automotive interior parts, automotive trim, signs, thermoformed letters, wallboard, toys, thermally conductive plastics, ophthalmic lenses, tools, tool handles, and household items. In another embodiment, the compositions of the present disclosure are formed into films, sheets, fibers, formed articles, molded articles, formed parts, molded parts, medical devices, dental trays, dental instruments, containers, food containers, shipping containers, packaging, bottles, bottle closures, eyeglass frames, cutlery, disposable cutlery, cutlery handles, shelves, shelf dividers, furniture parts, electronics enclosures, electronics cases, computer monitors, printers, keyboards, tubing, toothbrush handles, automotive parts, automotive interior parts, automotive trim, signs, outdoor signs, skylights, multi-walled layer films, multi-layer films, insulation parts, insulation articles, insulated containers, thermoformed letters, wallboard, toys, toy parts, trays, food trays, teeth Suitable for use as medical trays, thermally conductive plastics, ophthalmic lenses and frames, tools, tool handles, and household items, healthcare products, commercial food supply products, boxes, graphic arts film, plastic film for plastic glazing laminates, point of purchase signs, skylights, smoke vents, laminated cards, fenestration, glazing, dividers, ceiling tiles, lighting, machine guards, graphic arts, lenses, extruded laminate sheet or film, decorative laminates, office furniture, face shields, medical packaging, shelf sign holders, and shelf price holders.

[0166]

[0178] The thermoformable or thermoformable sheets of the present disclosure are useful for forming films, formed articles, formed parts, molded articles, molded parts, and sheets. The thermoformable or thermoformable compositions can be manufactured into films, formed articles, formed parts, molded articles, molded parts, and sheets by any method known in the art. Examples of formed articles include, but are not limited to, medical device packaging, medical packaging, healthcare products, trays, containers, food plates, tumblers, storage boxes, bottles, food processors, commercial food service products such as blenders and mixing bowls, household products, water bottles, crisper trays, washing machine parts, refrigerator parts, vacuum cleaner parts, ophthalmic lenses and frames, and toys.

[0167]

[0179] The present disclosure further relates to articles of manufacture comprising sheets comprising the polyester compositions described herein. In embodiments, the sheets of the present disclosure may be of any thickness required for the intended use.

[0168]

[0180] The present disclosure further relates to the sheets described herein. Methods for forming the polyester composition into a sheet include any method known in the art. Examples of sheets of the present disclosure include, but are not limited to, extrusion sheets, calendered sheets, compression molded sheets, and solution cast sheets. Methods for making sheets of the present disclosure include, but are not limited to, extrusion, calendering, compression molding, wet blocking, dry blocking, and solution casting.

[0169]

[0181] The present disclosure further relates to the formed or molded articles described herein. Methods for forming the polyester composition into formed or molded articles include any method known in the art. Examples of formed or molded articles of the present disclosure include, but are not limited to, thermoformed or thermoformable articles, injection molded articles, extrusion molded articles, injection blow molded articles, injection stretch blow molded articles, and extrusion blow molded articles. Methods for producing formed articles include, but are not limited to, thermoforming, injection molding, extrusion, injection blow molding, injection stretch blow molding, and extrusion blow molding. The process of the present disclosure may include any thermoforming process known in the art. The process of the present disclosure may include any blow molding process known in the art, including, but not limited to, extrusion blow molding, extrusion stretch blow molding, injection blow molding, and injection stretch blow molding.

[0170]

[0182] This disclosure includes any injection blow molding manufacturing process known in the art. A typical injection blow molding (IBM) manufacturing process includes, but is not limited to, the steps of: 1) melting a composition in a reciprocating screw extruder, 2) injecting the molten composition into an injection mold to form a partially cooled tube (i.e., a preform) closed at one end, 3) transferring the preform into a blow mold having the desired final shape around the preform and closing the blow mold around the preform, 4) blowing air into the preform to stretch and expand it to fill the mold, 5) cooling the molded article, and 6) removing the article from the mold.

[0171]

[0183] This disclosure includes any injection stretch blow molding manufacturing process known in the art. A typical injection stretch blow molding (ISBM) manufacturing process includes, but is not limited to, the steps of: 1) melting a composition in a reciprocating screw extruder, 2) injecting the molten composition into an injection mold to form a partially cooled tube (i.e., a preform) closed at one end, 3) transferring the preform to a blow mold having the desired final shape around the preform and closing the blow mold around the preform, 4) stretching the preform with an internal stretch rod to blow air into the preform and stretch and expand it to fill the mold, 5) cooling the molded article, and 6) removing the article from the mold.

[0172]

[0184] This disclosure includes any extrusion blow molding manufacturing process known in the art. A typical extrusion blow molding manufacturing process includes, but is not limited to, the steps of: 1) melting a composition in an extruder, 2) extruding the molten composition through a die to form a tube of molten polymer (i.e., a parison), 3) clamping a mold having the desired final shape around the parison, 4) blowing air into the parison to stretch and expand the extrudate to fill the mold, 5) cooling the molded article, 6) removing the article from the mold, and 7) removing excess plastic (commonly referred to as flash) from the article.

[0173]

[0185] The following examples further illustrate how the polyesters of the present disclosure can be made and evaluated, and are intended to be purely illustrative and not limiting in scope. Unless otherwise indicated, parts are parts by weight, temperature is in degrees Celsius or is room temperature, and pressure is atmospheric or near atmospheric.

[0174]

[0186] The present disclosure includes and expressly contemplates and discloses any and all combinations of the embodiments, features, properties, parameters, and / or ranges described herein, i.e., the subject matter of the present disclosure can be defined by any combination of the embodiments, features, properties, parameters, and / or ranges described herein.

[0175]

[0187] Any process / method, apparatus, compound, composition, embodiment, or component of the present disclosure may be modified by the transitional phrases "comprising," "consisting essentially of," or "consisting of," or variations of these terms.

[0176]

[0188] As used herein, the indefinite articles "a" and "an" refer to one or more, unless the context clearly dictates otherwise. Similarly, the singular form of a noun includes its plural and vice versa, unless the context clearly dictates otherwise.

[0177]

[0189] Although attempts have been made to achieve accuracy, the numerical values ​​and ranges set forth herein should be considered approximations unless the context otherwise dictates. These numerical values ​​and ranges may vary from the stated numerical values ​​depending on the desired properties sought to be obtained by the present disclosure and variations due to standard deviations encountered in measurement techniques. Furthermore, ranges set forth herein are intended to include and are specifically contemplated as including all subranges and numerical values ​​within the stated range. For example, a range of 50 to 100 is intended to include all numerical values ​​within that range, including subranges such as 60 to 90, 70 to 80, etc.

[0178]

[0190] Any two numerical values ​​for the same characteristic or parameter reported in the examples may define a range, and those numerical values ​​may be rounded to the nearest thousandth, hundredth, tenth, whole number, ten, hundred, or thousand to define the range.

[0179]

[0191] The contents of all documents cited herein, including patent and non-patent literature, are incorporated herein by reference in their entirety. In the event that any incorporated subject matter conflicts with any disclosure herein, the disclosure herein takes precedence over the incorporated content.

[0180]

[0192] The present disclosure can be further illustrated by the following examples, which, of course, are included for illustrative purposes only and are not intended to limit the scope of the disclosure. [Example]

[0181]

[0193] The oligomers used in these examples were prepared in a batch test facility and used as is. The composition evaluated was a copolymer of terephthalic acid, ethylene glycol, 1,4-cyclohexanedimethanol, diethylene glycol, and neopentyl glycol. The glycol concentrations were 13 mol % NPG, 3 mol % 1,4-cyclohexanedimethanol, and 5 mol % diethylene glycol, with the remaining 79 mol % being ethylene glycol. The oligomers were prepared with a molar ratio of total glycols to terephthalic acid of 1.55, based on the weight of all glycols charged.

[0182]

[0194] Each polyester sample was prepared by placing enough oligomer to produce 100 g of polyester into a 500 mL, one-neck, round-bottom flask. The target concentrations of titanium and antimony catalysts were added to the flask as ethylene glycol solutions, along with the desired concentration of phosphorus. A stainless steel stirring apparatus consisting of a 2.5-inch diameter impeller attached to a 1 / 4-inch diameter shaft was inserted into the flask, and a glass polymer head was then attached to the flask. A polymer head consisting of a standard tapered 24 / 40 male fitting was attached to the reaction flask. The flask was equipped with a side arm positioned approximately 45° to the flask neck to allow for the removal of volatiles, and a section of glass tubing extending above the flask neck through which the stirring shaft passed. The stirring shaft was fitted with a Teflon bushing and rubber hose, creating a vacuum seal around the stirring shaft. The shaft was rotated by a 1 / 8 horsepower motor connected to the shaft using a flexible "universal" joint. The side arm was connected to a vacuum system consisting of a dry-ice cooled condenser and a vacuum pump. The pressure inside the reaction flask was controlled by flowing nitrogen into the vacuum line. The reaction flask was heated using a molten metal bath. All reaction parameters were monitored and controlled using a distributed data acquisition and control system.

[0183]

[0195] Table 1 shows the reaction sequence used in all cases to prepare the polyester samples included in this evaluation.

[0184] [Table 1]

[0185]

[0196] Following synthesis, each polymer was removed from the stirrer blades and ground in a hammer mill to a particle size small enough to pass through a sieve with 6 mm openings. All testing was performed on these granules without further processing.

[0186]

[0197] Table 2 below includes eight control compositions prepared with a titanium-only catalyst system and several examples of catalyst systems of the present disclosure at various temperatures.

[0187] [Table 2]

[0188]

[0198] The data in Table 2 show that the average b * is about 20. However, b * The data are improved for all catalyst systems using Ti (5-15 ppm) and P (5-50 ppm) in combination with Sb (110-125 ppm). These results demonstrate that the polymers of the present invention are superior to the control resin made with titanium alone. * At the standard polymerization temperature of 280°C, the intrinsic viscosity is the same, but b * is improved to less than 20. At higher temperatures (290°C and 300°C), IV and b * Both of these have been improved, resulting in a higher intrinsic viscosity and * is still below 20.

[0189]

[0199] The intrinsic viscosity of the polyesters herein is measured in 60 / 40 (wt / wt) phenol / tetrachloroethane at 25° C. and a concentration of 0.5 g / dL and is reported in dL / g.

[0190]

[0200] Copolyester resin samples were prepared using the procedures described herein. In all cases, the resin samples were dried before extrusion.

[0201] Test film samples were prepared by extruding the resin samples into 10 mil (250 μm) films using a 2.5 inch Davis and Standard single screw extruder. These 10 mil films were cut and then extruded on a Bruckner Karo 4 tenter frame. ) at a temperature 5-15°C above the glass transition temperature (Tg) of the extruded film and a draw ratio of about 5:1 to a final thickness of 50 µm.

[0191]

[0202] Tenter film samples were prepared by extruding resin samples and stretching them on a commercially available tenter (located at Marshall and Williams, a division of Parkinson Technologies). The film was extruded with three layers from an ABC die, with the B layer extruded through a 2.5-inch single-screw extruder and the A and C layers extruded through separate 1.25-inch single-screw satellite extruders. The film was cast at approximately 10 mils (250 μm) thickness and then stretched to 50 μm thickness at a 5:1 draw ratio. Typically, the cast thickness is 250 μm and the final film thickness is 50 μm. The line speed was 45 fpm.

[0192]

[0203] The glycol content of the extruded film compositions was measured by NMR. All NMR spectra were recorded on a JEOL Eclipse Plus 600 MHz nuclear magnetic resonance spectrometer using chloroform-trifluoroacetic acid (70-30:vol / vol) for all polymers with deuterated chloroform added for locking. The acid component of the mixed polymers used in the examples herein was 100 mol% terephthalic acid. The total mol% of glycol components was equal to 100 mol%, and the total mol% of acid components was equal to 100 mol%.

[0193]

[0204] The intrinsic viscosity of the polyesters herein is measured in 60 / 40 (wt / wt) phenol / tetrachloroethane at 25° C. and a concentration of 0.5 g / dL and is reported in dL / g.

[0194]

[0205] Shrinkage is measured herein by placing a 50 mm x 50 mm square film sample in water at temperatures between 65°C and 95°C in 5°C increments. The film is immersed in water for 10 seconds without restricting shrinkage in either direction, and the shrinkage (or expansion) of the film sample is measured. Shrinkage is calculated using the following formula:

[0195] Shrinkage rate (%) = [(50 mm - length after shrinkage) / 50 mm] x 100%

[0206] Shrinkage was measured in the direction perpendicular to the main shrinkage direction (machine direction: MD) and also in the main shrinkage direction (transverse direction: TD).

[0196]

[0207] Shrinkage force was measured in MPa using a LabThink FST-02 heat shrinkage tester at the same temperatures used to stretch the films for the examples herein.

[0208] Tensile film properties were measured for the examples herein using ASTM method D882. Multiple film stretching speeds (300 mm / min and 500 mm / min) were used to evaluate film toughness.

[0197]

[0209] The glass transition temperature and strain-induced crystalline melting point (Tg and Tm, respectively) of the polyester were measured using a Thermal Analyst Instrument TA DSC 2920 at a scan rate of 20°C / min. Tm was measured on the first heat of the stretched sample, and Tg was measured on the second heat step. Additionally, samples can be crystallized at 165°C for 30 minutes in a forced air oven and then analyzed by DSC. For all samples, the crystalline melting point was generally absent during the second heat of the DSC scan at a heating rate of 20°C / min.

[0198]

[0210] The suitability of materials for recycling processes is governed by procedures published by the Association of Plastics Recyclers (APR). In the case of PETG resins, PET clumping is the primary issue addressed by this invention. A laboratory process was developed to mimic this industry standard. The experimental clumping test parameters are as follows: Combine 582g of PET flakes with 18g of shrinkable film (3% film relative to the PET flakes) in its shrunk state (the film was immersed in 85°C water for 10 seconds to shrink it before combining). The PET flakes + film were placed in an aluminum dish to a depth of 1.5 inches. The dish containing the slices was placed in a forced air oven at 208°C for 1.5 hours. The flakes were then carefully poured through a 0.5 inch sieve and the amount of flakes that remained in the dish or failed to pass through the sieve was measured and the percent agglomeration was calculated as a percentage of the starting weight.

[0199]

[0211] The Association of Plastic Recyclers (APR) has established a test to determine whether materials comply with current recycling processes (Important Instructions for Clear PET Articles with Labels and Seals, revised or established on April 11, 2019; PET-CG-02). This method references a method for measuring PET cohesion (PET Flake Cohesion Assessment, revised on November 16, 2018; PET-S-08). Details of this test are as follows: Labeled bottle flakes are prepared by crushing the label (minimum weight: 3% by weight, pre-shrunk at 85°C for 10 seconds) and bottle into flakes measuring 1 / 4 to 1 / 2 inch. · Mix labeled bottle slices 50:50 with unlabeled reference bottle slices. · The samples were then wet classified under conditions that allowed no more than 1.2% of the PET to be carried over with the label. The slices are then washed in 0.3% Triton X-100 and 1.0% caustic at 88°C for 15 minutes. The flakes are then washed with water after removing all suspended solids and then filtered to remove excess water. · Wet classify the flakes again as before. Place 2 pounds of cleaned slices (including labels) into a Teflon-coated baking dish for each cleaned sample, adding slices to a layer 1.5 inches thick. Place the dish containing the slices in a circulating oven at 208°C for 1.5 hours. The flakes are cooled and then passed through a sieve with 0.0625 inch openings. If the material passes through the sieve, it is not agglomerated, i.e., it is not too coarse to pass through the sieve. This test was followed by an extrusion / pelletization and molding process to confirm the quality of the flakes.

[0200]

[0212] Modulated differential scanning calorimetry (MDSC) is a technique that measures the difference in heat flow between a sample and an inert reference as a function of time and temperature. Furthermore, it uses the same heat flux cell design as used in conventional DSC. However, in MDSC, a different heating regime (temperature regime) is applied to the sample and reference. Specifically, a sinusoidal modulation (amplitude) is superimposed on a conventional linear heating or cooling ramp, producing a regime in which the average sample temperature varies continuously, but not linearly, with time. The net effect of applying this more complex heating regime to a sample is as if two tests were performed simultaneously on the material: one with a conventional linear (average) heating rate and one with a sinusoidal (instantaneous) heating rate. The actual rate of these two simultaneous tests depends on three operator-selectable variables: · Base heating rate (3°C / min) Modulation period (60 seconds) Temperature amplitude of modulation (±1℃)

[0213] Reversing heat flow was used to analyze the glass transition temperature and the area of ​​the melting peak. The heat of fusion (Hf) upon heating was measured as the integrated reversing heat flow signal. The heat of crystallization (Hc) upon heating was integrated from the total heat flow signal. The relative crystallinity (C) of the sample was determined by subtracting the heat of fusion (Hf) from the heat of crystallization (Hc) upon heating.

[0201] Examples 1 to 4

[0214] Copolyester resins with various glycol compositions were made and converted into shrinkable films using an experimental film process, and the corresponding shrinkable film properties were measured. Film samples were also tested for clumping with PET flakes using an experimental clumping test. Key performance properties are listed below. Films made with resin examples 1 and 2 had less than 1% clumping of PET flakes. Films made with resin examples 1, 3, and 4 had excellent shrinkable film properties. Only the film made with resin example 1 had excellent shrinkable film properties and less than 1% clumping.

[0202] [Table 3]

[0203]

[0215] Examples 5 to 7 Resin Examples 5-7 were made, converted into shrinkable films on a commercial tentering machine, and tested for suitability for PET recycling using the APR test procedure.

[0204] [Table 4]

[0205]

[0216] Examples 8 to 11 Resins based on Examples 8-11 were converted into shrink film samples and tested for shrink film properties and for clumping with PET flakes using an experimental clumping test.

[0206] [Table 5]

[0207]

[0217] Examples 12 to 16 Multilayer films were made using a commercial tenter frame process and tested for cohesion with PET flakes using an experimental cohesion test. These films were made with Example 4 as the core layer and Example 1 as the cap layer.

[0208] [Table 6]

[0209] Examples of thermoformed sheets:

[0218] Examples A, B, and C were extruded into 30 mil (750 μm) thick sheet material using a 2.5-inch Davis and Standard extruder. The sheet samples were then thermoformed into the basic tray shape (dimensions: 169 mm x 136 mm x 44 mm) using an aluminum female die designed to allow vacuum to be drawn throughout the shape. This die was attached to a Hydrotrim laboratory thermoforming machine. The oven and die temperatures were held constant at 260°C and 42°C, respectively. The sheet samples were placed in the oven for various residence times, removed from the oven, immediately formed into trays, and cooled before being removed from the die. The temperature of the sheet was measured using an infrared temperature sensor that was part of the thermoforming machine and confirmed with a handheld infrared thermometer.

[0210]

[0219] The dwell time was varied, starting at 15 seconds and increasing by 2 seconds each time, to identify the range of thermoforming conditions that would produce high-quality parts. The dwell time was varied so that the samples were heated to different temperatures before molding. The test was stopped after a dwell time of 29 seconds was reached because Example C became too turbid to be considered a production-ready tray. The turbidity of each sample was measured as an indicator of part quality and crystallization.

[0211]

[0220] The tray made from Example C began to show slight haze at a residence time of 23 seconds. This indicates a smaller thermoforming range for Example C compared to Examples A and B, as Examples A and B did not show an increase in haze over this range of residence times. The quality of the thermoformed parts is indicated by a "+" indicating acceptable quality or a "-" indicating poor quality. These quality ratings are based on a combination of post-thermoforming haze and part precision.

[0212]

[0221] Samples of extruded sheet and thermoformed parts were evaluated for suitability for PET recycling using an experimental agglomeration procedure. In addition, a pre-crystallization step was used as described in the APR screening test for PET agglomeration. The results of this agglomeration test are presented below.

[0213]

[0222] Example B exhibits desirable and differentiated properties, namely, a wider range of thermoforming conditions making it easier to process, and compatibility with PET recycling processes, allowing for crystallization during the recycling process.

[0214] [Table 7]

[0215] [Table 8]

[0216] [Table 9]

[0217] Injection molding samples:

[0223] Samples A, B, C, and Examples 1 and 3 were injection molded and tested for their mechanical properties using conventional injection molding procedures known to those skilled in the art. Test parts were tested according to ASTM Method D638, ASTM Method D3763, ASTM Method D256, ASTM Method D4812, and ASTM Method D64. The mechanical properties of injection molded parts made with these reactor grade resins are shown in Table 10.

[0218] [Table 10]

[0219]

[0224] While the present disclosure has been described in detail with particular reference to preferred embodiments thereof, It will be appreciated that numerous changes and modifications can be made within the spirit and scope of the disclosure. The following are embodiments: Aspect 1 1. A crystallizable reactor grade polyester composition comprising at least one polyester, said at least one polyester comprising: (a) a dicarboxylic acid component containing: (i) about 70 to about 100 mole percent terephthalic acid residues, and (ii) from about 0 to about 30 mole percent of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a diol component comprising: greater than or equal to about 75 mole percent ethylene glycol residues, and About 25 mole % or less of other glycols containing one or more of the following: (i) from about 0.1 to less than about 24 mole percent neopentyl glycol residues; (ii) from about 0.1 to less than about 24 mole percent 1,4-cyclohexanedimethanol residues, and (iii) from about 1 to less than about 10 mole percent total diethylene glycol residues in the final polyester composition wherein the total mole % of said dicarboxylic acid components is 100 mole % and the total mole % of said diol components is 100 mole %. Aspect 2 1. A crystallizable reactor grade polyester composition comprising at least one polyester, said at least one polyester comprising: (a) a dicarboxylic acid component containing: (i) about 70 to about 100 mole percent terephthalic acid residues, and (ii) from about 0 to about 30 mole percent of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a diol component comprising: greater than or equal to about 80 mole percent ethylene glycol residues, and About 20 mol% or less of other glycols containing one or more of the following: (i) from about 5 to less than about 17 mole percent neopentyl glycol residues; (ii) from about 2 to less than about 10 mole percent 1,4-cyclohexanedimethanol residues, and (iii) from about 1 to less than about 5 mole percent total diethylene glycol residues in the final polyester composition Including, A crystallizable reactor grade polyester composition, wherein the total mole % of said dicarboxylic acid components is 100 mole % and the total mole % of said diol components is 100 mole %. Aspect 3 the reactor grade polyester composition further comprises the residue of a catalyst system comprising 2 to 15 ppm titanium, 50 to 150 ppm antimony, and 0 to 90 ppm phosphorus, the concentration of the residue of the catalyst system being based on the weight of the polyester; or the reactor grade polyester composition further comprises the residue of a catalyst system comprising 3 to 10 ppm titanium, 50 to 125 ppm antimony, and 0 to 60 ppm phosphorus, the concentration of the residue of the catalyst system being based on the weight of the polyester; or 3. The crystallizable reactor grade polyester composition of claim 1 or 2, wherein the reactor grade polyester composition further comprises residues of a catalyst system comprising 4 to 12 ppm titanium, 100 to 120 ppm antimony, and 2 to 50 ppm phosphorus, the concentration of the residues of the catalyst system being based on the weight of the polyester. Aspect 4 3. The crystallizable reactor grade polyester composition of claim 1 or 2, wherein the strain-induced crystallinity of the reactor grade polyester composition has a melting point of 190° C. or higher. Aspect 5 3. The crystallizable reactor grade polyester composition of claim 1 or 2, wherein the strain-induced crystallinity of the reactor grade polyester composition has a melting point of 200° C. or higher. Aspect 6 1. A process for preparing a crystallizable reactor grade polyester composition, comprising: (a) reacting a diacid component containing a terephthalic acid residue with a diol component containing a neopentyl glycol residue, a 1,4-cyclohexanedimethanol residue, a diethylene glycol residue, and an ethylene glycol residue in the presence of 2 to 15 ppm of a titanium compound and 50 to 150 ppm of an antimony compound at a temperature of 240 to 270°C and a pressure of 5 to 50 psi to produce an esterification product; (b) prepolymerizing the esterified product in the presence of 0 to 90 ppm of a phosphorus stabilizer at a temperature of 255 to 275°C and a pressure of 200 to 500 mmHg to produce a polycondensation product; and (c) finishing the polycondensation product to produce a polyester; The polyester has an intrinsic viscosity of at least 0.50 dL / g or 0.50-0.90 dL / g, and the polymerization temperature during the finishing treatment is increased to 280-320°C and the pressure is 0.3-7 mmHg. Aspect 7 1. A process for preparing a crystallizable reactor grade polyester composition, comprising: (a) reacting a diacid component comprising terephthalic acid residues with a diol component comprising neopentyl glycol residues, 1,4-cyclohexanedimethanol residues, diethylene glycol residues, and ethylene glycol residues at a temperature of 240-270°C and a pressure of 5-50 psi to produce an esterification product; (b) prepolymerizing the esterified product in the presence of 2 to 15 ppm of a titanium compound, 50 to 150 ppm of an antimony compound, and 0 to 90 ppm of a phosphorus stabilizer at a temperature of 255 to 275°C to produce a preliminary polycondensation product; and (c) finishing the polycondensation product to produce a polyester; The polyester has an intrinsic viscosity of at least 0.50 dL / g or 0.50-0.90 dL / g, and the polymerization temperature during the finishing treatment is increased to 280-320°C and the pressure is 0.3-7 mmHg. Aspect 8 the titanium compound is selected from titanium tetraalkoxides such as titanium tetraisopropoxide, titanium tetraethoxide, or titanium tetrabutoxide, or titanic acid tetraalkyl esters such as tetraisopropyl titanate, and mixtures thereof; or the antimony compound is one or more of antimony trioxide, antimony acetate, or antimony oxalate; or 8. The catalyst system of claim 6 or 7, wherein the phosphorus-containing compound is a phosphate ester such as a trialkyl phosphate, an alcohol phosphate, a triphenyl phosphate, or a trisnonylphenyl phosphite, or phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphonous acid, and various esters and salts thereof. Aspect 9 8. The process of claim 6 or 7, further comprising dissolving the antimony compound in one of a glycol. Aspect 10 8. The process of claim 6 or 7, wherein the polymerization temperature during the finish treatment is 290°C or 300°C. Aspect 11 8. The process of embodiment 6 or 7, wherein the titanium component and the antimony component are added together, and the phosphorus component is added as a separate feed. Aspect 12 1. A catalyst system for producing a crystallizable reactor grade polyester composition, comprising: 2 to 15 ppm of titanium compounds, 50 to 150 ppm of antimony compounds, and Contains 0 to 90 ppm of phosphorus compounds, The polyester composition comprises a catalyst system including terephthalic acid, 1,4-cyclohexanedimethanol, neopentyl glycol, ethylene glycol, and diethylene glycol. Aspect 13 13. The catalyst system of embodiment 12, wherein the titanium compound and the antimony compound are added together and phosphorus acts as a stabilizer and is added as a separate feed subsequent to the addition of the catalyst. Aspect 14 13. The catalyst system of embodiment 12, wherein the titanium compound, the antimony compound, and the phosphorus compound are added subsequent to the esterification of the terephthalic acid. Aspect 15 The phosphorus compound is a phosphoric acid ester such as trialkyl phosphate, alcohol phosphate, triphenyl phosphate, or trisnonylphenyl phosphite, or phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphonous acid, and various esters and salts thereof; or the titanium compound is selected from titanium tetraalkoxides such as titanium tetraisopropoxide, titanium tetraethoxide, or titanium tetrabutoxide, or titanic acid tetraalkyl esters such as tetraisopropyl titanate, and mixtures thereof; or 13. The catalyst system of embodiment 12, wherein the antimony compound is one or more of antimony trioxide, antimony acetate, or antimony oxalate. Aspect 16 13. The catalyst system of embodiment 12, wherein the antimony compound is dissolved in one of the glycols, or the titanium compound is dissolved in one of the glycols or butanol. Aspect 17 1. A crystallizable film comprising a polyester composition comprising at least one polyester, said at least one polyester comprising: (a) a dicarboxylic acid component containing: (i) about 70 to about 100 mole percent terephthalic acid residues, and (ii) from about 0 to about 30 mole percent of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; (b) a diol component comprising: greater than or equal to about 75 mole percent ethylene glycol residues, and About 25 mole % or less of other glycols containing one or more of the following: (i) from about 0.1 to less than about 24 mole percent neopentyl glycol residues; (ii) 0 to less than about 24 mole percent 1,4-cyclohexanedimethanol residues, and (iii) from about 1 to less than about 10 mole percent total diethylene glycol residues in the final polyester composition and (c) a catalytic system residue comprising: 2-15 ppm titanium, 50-150 ppm antimony, and 0-90 ppm phosphorus wherein the total mole % of the dicarboxylic acid components is 100 mole % and the total mole % of the diol components is 100 mole %; the concentration of the catalyst system residue is based on the weight of the polyester; The polyester has an intrinsic viscosity of 0.68-0.75 dL / g when measured in 60 / 40 (wt / wt) phenol / tetrachloroethane at 25°C and a concentration of 0.5 g / dL, and the polyester is measured using a TA DSC 2920 manufactured by Thermal Analyst Instruments. A crystallizable film having a Tg of 72°C to 77°C when measured using a scanning rate of 20°C / min. Aspect 18 1. A crystallizable film comprising a polyester composition comprising at least one polyester, said at least one polyester comprising: (a) a dicarboxylic acid component containing: (i) about 70 to about 100 mole percent terephthalic acid residues, and (ii) from about 0 to about 30 mole percent of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; (b) a diol component comprising: greater than or equal to about 80 mole percent ethylene glycol residues, and About 20 mol% or less of other glycols containing one or more of the following: (i) from about 5 to less than about 17 mole percent neopentyl glycol residues; (ii) from about 2 to less than about 10 mole percent 1,4-cyclohexanedimethanol residues, and (iii) from about 1 to less than about 5 mole percent total diethylene glycol residues in the final polyester composition and (c) a catalytic system residue comprising: 2-15 ppm titanium, 50-150 ppm antimony, and 0-90 ppm phosphorus wherein the total mole % of the dicarboxylic acid components is 100 mole % and the total mole % of the diol components is 100 mole %; the concentration of the catalyst system residue is based on the weight of the polyester; The polyester has an intrinsic viscosity of 0.68-0.75 dL / g when measured in 60 / 40 (wt / wt) phenol / tetrachloroethane at 25°C and a concentration of 0.5 g / dL, and the polyester is measured using a TA DSC 2920 manufactured by Thermal Analyst Instruments. A crystallizable film having a Tg of 72°C to 77°C when measured using a scanning rate of 20°C / min. Aspect 19 1. A crystallizable film comprising a polyester composition comprising at least one polyester, said at least one polyester comprising: (a) a dicarboxylic acid component containing: (i) about 70 to about 100 mole percent terephthalic acid residues, and (ii) from about 0 to about 30 mole percent of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; (b) a diol component comprising: greater than or equal to about 76 mole percent ethylene glycol residues, and About 24 mol% or less of amorphous components containing one or more of the following: (i) a neopentyl glycol residue, (ii) a cyclohexanedimethanol residue, and (iii) diethylene glycol residues in the final polyester composition and (c) a catalytic system residue comprising: 2-15 ppm titanium, 50-150 ppm antimony, and 0-90 ppm phosphorus wherein the total mole % of the dicarboxylic acid components is 100 mole % and the total mole % of the diol components is 100 mole %; the concentration of the catalyst system residue is based on the weight of the polyester; The polyester has an intrinsic viscosity of 0.68-0.75 dL / g when measured in 60 / 40 (wt / wt) phenol / tetrachloroethane at 25°C and a concentration of 0.5 g / dL, and the polyester is measured using a TA DSC 2920 manufactured by Thermal Analyst Instruments. A crystallizable film having a Tg of 72°C to 77°C when measured using a scanning rate of 20°C / min. Aspect 20 1. A crystallizable film comprising a polyester composition comprising at least one polyester, said at least one polyester comprising: (a) a dicarboxylic acid component containing: (i) about 70 to about 100 mole percent terephthalic acid residues, and (ii) from about 0 to about 30 mole percent of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; (b) a diol component comprising: (i) about 1 to about 30 mole % neopentyl glycol residues; (ii) from about 1 to less than about 30 mole percent 1,4-cyclohexanedimethanol residues, and (iii) about 1.5 to 6 mole percent diethylene glycol residues wherein the remainder of the glycol component is (iv) ethylene glycol residues, and (v) containing 0 to 20 mol % of at least one modifying glycol residue and (c) a catalytic system residue comprising: 2-15 ppm titanium, 50-150 ppm antimony, and 0-90 ppm phosphorus wherein the total mole % of the dicarboxylic acid components is 100 mole % and the total mole % of the diol components is 100 mole %; the concentration of the catalyst system residue is based on the weight of the polyester; The polyester has an intrinsic viscosity of 0.68-0.75 dL / g when measured in 60 / 40 (wt / wt) phenol / tetrachloroethane at 25°C and a concentration of 0.5 g / dL, and the polyester is measured using a TA DSC 2920 manufactured by Thermal Analyst Instruments. A crystallizable film having a Tg of 72°C to 77°C when measured using a scanning rate of 20°C / min.

Claims

1. 1. A crystallizable reactor grade polyester composition comprising at least one polyester, said at least one polyester comprising: (a) a dicarboxylic acid component comprising: (i) 70 to 100 mole percent terephthalic acid residues, and (ii) 0 to 30 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms and (b) a diol component comprising: 75 mole percent or more ethylene glycol residues, and Up to 25 mole percent of other glycols, including: (i) 0.1 to less than 24 mole percent neopentyl glycol residues; (ii) from 0.1 to less than 24 mole percent of 1,4-cyclohexanedimethanol residues; and (iii) 1 to less than 10 mole percent total diethylene glycol residues in the final polyester composition; the total mole percent of the dicarboxylic acid component is 100 mole percent, and the total mole percent of the diol component is 100 mole percent; the crystallizable reactor grade polyester composition comprises a catalyst system residue comprising 2 to 15 ppm titanium, 50 to 150 ppm antimony, and 2 to 90 ppm phosphorus; or a catalyst system residue containing 3-10 ppm titanium, 50-125 ppm antimony, and 2-60 ppm phosphorus; or a catalyst system residue comprising 4 to 12 ppm titanium, 100 to 120 ppm antimony, and 2 to 50 ppm phosphorus; the concentration of the catalyst system residue is based on the weight of the polyester; Crystallizable reactor grade polyester composition.

2. 1. A crystallizable reactor grade polyester composition comprising at least one polyester, said at least one polyester comprising: (a) a dicarboxylic acid component comprising: (i) 70 to 100 mole percent terephthalic acid residues, and (ii) 0 to 30 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms and (b) a diol component comprising: 80 mole percent or more ethylene glycol residues, and Up to 20 mole percent of other glycols, including: (i) 5 to less than 17 mole percent neopentyl glycol residues; (ii) 2 to less than 10 mole percent 1,4-cyclohexanedimethanol residues, and (iii) 1 to less than 5 mole percent total diethylene glycol residues in the final polyester composition; the total mole percent of the dicarboxylic acid component is 100 mole percent, and the total mole percent of the diol component is 100 mole percent; the crystallizable reactor grade polyester composition comprises a catalyst system residue comprising 2 to 15 ppm titanium, 50 to 150 ppm antimony, and 2 to 90 ppm phosphorus; or a catalyst system residue containing 3-10 ppm titanium, 50-125 ppm antimony, and 2-60 ppm phosphorus; or a catalyst system residue comprising 4 to 12 ppm titanium, 100 to 120 ppm antimony, and 2 to 50 ppm phosphorus; the concentration of the catalyst system residue is based on the weight of the polyester; Crystallizable reactor grade polyester composition.

3. 3. The crystallizable reactor grade polyester composition according to claim 1, wherein the strain-induced crystallization melting point of the reactor grade polyester composition is 190°C or higher.

4. 3. The crystallizable reactor grade polyester composition according to claim 1, wherein the melting point of strain-induced crystallization of the reactor grade polyester composition is 200°C or higher.

5. 1. A process for preparing a crystallizable reactor grade polyester composition, comprising: (a) reacting a diacid component comprising terephthalic acid residues with a diol component comprising neopentyl glycol residues, 1,4-cyclohexanedimethanol residues, diethylene glycol residues, and ethylene glycol residues in the presence of 2 to 15 ppm of a titanium compound and 50 to 150 ppm of an antimony compound at a temperature of 240 to 270°C and a pressure of 5 to 50 psi to produce an esterification product; (b) prepolymerizing the esterification product in the presence of 2 to 90 ppm of a phosphorus stabilizer at a temperature of 255 to 275°C and a pressure of 200 to 500 mmHg to produce a polycondensation product; and (c) finishing the polycondensation product to produce a polyester; The polyester has an intrinsic viscosity of at least 0.50 dL / g or 0.50-0.90 dL / g, and the polymerization temperature during the finishing treatment is increased to 280-320° C. and the pressure is 0.3-7 mmHg.

6. 1. A process for preparing a crystallizable reactor grade polyester composition, comprising: (a) reacting a diacid component comprising terephthalic acid residues with a diol component comprising neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol, and ethylene glycol residues at a temperature of 240-270°C and a pressure of 5-50 psi to produce an esterification product; (b) prepolymerizing the esterified product in the presence of 2 to 15 ppm of a titanium compound, 50 to 150 ppm of an antimony compound, and 2 to 90 ppm of a phosphorus stabilizer at a temperature of 255 to 275°C to produce a pre-polycondensation product; and (c) finishing the pre-polycondensation product to produce a polyester; The polyester has an intrinsic viscosity of at least 0.50 dL / g or 0.50-0.90 dL / g, and the polymerization temperature during the finishing treatment is increased to 280-320° C. and the pressure is 0.3-7 mmHg.

7. the titanium compound is selected from titanium tetraalkoxides, or titanium acid tetraalkyl esters, and mixtures thereof; or the antimony compound is one or more of antimony trioxide, antimony acetate, or antimony oxalate; or 7. The process of claim 5 or 6, wherein the phosphorus stabilizer is a phosphate ester, or phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphonous acid, and their various esters and salts.

8. 7. The process of claim 5 or 6, further comprising the step of dissolving the antimony compound in one of the diol components.

9. 7. The process according to claim 5 or 6, wherein the polymerization temperature during the finishing treatment is 290°C or 300°C.

10. 7. The process of claim 5 or 6, wherein the titanium compound and the antimony compound are added together and the phosphorus stabilizer is added as a separate feed.

11. 1. A catalyst system for producing a crystallizable reactor grade polyester composition, comprising: 2 to 15 ppm of titanium compounds, 50 to 150 ppm of antimony compounds, and containing 2 to 90 ppm of phosphorus compounds; The polyester composition comprises a catalyst system comprising terephthalic acid, 1,4-cyclohexanedimethanol, neopentyl glycol, ethylene glycol, and diethylene glycol.

12. 12. The catalyst system of claim 11 obtained by a process in which the titanium compound and the antimony compound are added together and phosphorus, which acts as a stabilizer, is added as a separate feed.

13. 12. The catalyst system of claim 11, wherein the titanium compound, the antimony compound, and the phosphorus compound are added subsequent to the esterification of the terephthalic acid.

14. The phosphorus compound is a phosphate ester, or phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphonous acid, and various esters and salts thereof; or the titanium compound is selected from titanium tetraalkoxides, or titanium acid tetraalkyl esters, and mixtures thereof; or 12. The catalyst system of claim 11, wherein the antimony compound is one or more of antimony trioxide, antimony acetate, or antimony oxalate.

15. 12. The catalyst system of claim 11, wherein the antimony compound is dissolved in one of 1,4-cyclohexanedimethanol, neopentyl glycol, ethylene glycol, and diethylene glycol, or the titanium compound is dissolved in one of 1,4-cyclohexanedimethanol, neopentyl glycol, ethylene glycol, and diethylene glycol or butanol.

16. 1. A crystallizable film comprising a polyester composition comprising at least one polyester, said at least one polyester comprising: (a) a dicarboxylic acid component comprising: (i) 70 to 100 mole percent terephthalic acid residues, and (ii) 0 to 30 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms (b) a diol component comprising: 75 mole percent or more ethylene glycol residues, and Up to 25 mole percent of other glycols, including: (i) 0.1 to less than 24 mole percent neopentyl glycol residues; (ii) from 0.1 to less than 24 mole percent of 1,4-cyclohexanedimethanol residues; and (iii) 1 to less than 10 mole percent total diethylene glycol residues in the final polyester composition and (c) a catalytic system residue comprising: 2 to 15 ppm titanium, 50 to 150 ppm antimony, and 2 to 90 ppm phosphorus Including, the total mole percent of the dicarboxylic acid component is 100 mole percent, and the total mole percent of the diol component is 100 mole percent; the concentration of the catalyst system residue is based on the weight of the polyester; The polyester has an intrinsic viscosity of 0.68 to 0.75 dL / g when measured in 60 / 40 (wt / wt) phenol / tetrachloroethane at 25° C. and a concentration of 0.5 g / dL, and the polyester is measured using a Thermal Analyst Instrument TA DSC 2920 A crystallizable film having a Tg of 72°C to 77°C as measured using a scanning rate of 20°C / min.

17. 1. A crystallizable film comprising a polyester composition comprising at least one polyester, said at least one polyester comprising: (a) a dicarboxylic acid component comprising: (i) 70 to 100 mole percent terephthalic acid residues, and (ii) 0 to 30 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms (b) a diol component comprising: 80 mole percent or more ethylene glycol residues, and Up to 20 mole percent of other glycols, including: (i) 5 to less than 17 mole percent neopentyl glycol residues; (ii) 2 to less than 10 mole percent 1,4-cyclohexanedimethanol residues, and (iii) 1 to less than 5 mole percent total diethylene glycol residues in the final polyester composition and (c) a catalytic system residue comprising: 2 to 15 ppm titanium, 50 to 150 ppm antimony, and 2 to 90 ppm phosphorus Including, the total mole percent of the dicarboxylic acid component is 100 mole percent, and the total mole percent of the diol component is 100 mole percent; the concentration of the catalyst system residue is based on the weight of the polyester; The polyester has an intrinsic viscosity of 0.68 to 0.75 dL / g when measured in 60 / 40 (wt / wt) phenol / tetrachloroethane at 25° C. and a concentration of 0.5 g / dL, and the polyester is measured using a Thermal Analyst Instrument TA DSC 2920 A crystallizable film having a Tg of 72°C to 77°C as measured using a scanning rate of 20°C / min.

18. 1. A crystallizable film comprising a polyester composition comprising at least one polyester, said at least one polyester comprising: (a) a dicarboxylic acid component comprising: (i) 70 to 100 mole percent terephthalic acid residues, and (ii) 0 to 30 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms (b) a diol component comprising: 76 mole percent or more ethylene glycol residues, and up to about 24 mole percent amorphous components including: (i) a neopentyl glycol residue, (ii) a cyclohexanedimethanol residue, and (iii) diethylene glycol residues in the final polyester composition and (c) a catalytic system residue comprising: 2 to 15 ppm titanium, 50 to 150 ppm antimony, and 2 to 90 ppm phosphorus Including, the total mole percent of the dicarboxylic acid component is 100 mole percent, and the total mole percent of the diol component is 100 mole percent; the concentration of the catalyst system residue is based on the weight of the polyester; The polyester has an intrinsic viscosity of 0.68 to 0.75 dL / g when measured in 60 / 40 (wt / wt) phenol / tetrachloroethane at 25° C. and a concentration of 0.5 g / dL, and the polyester is measured using a Thermal Analyst Instrument TA DSC 2920 A crystallizable film having a Tg of 72°C to 77°C as measured using a scanning rate of 20°C / min.

19. 1. A crystallizable film comprising a polyester composition comprising at least one polyester, said at least one polyester comprising: (a) a dicarboxylic acid component comprising: (i) 70 to 100 mole percent terephthalic acid residues, and (ii) 0 to 30 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms (b) a diol component comprising: (i) 1 to 30 mole % neopentyl glycol residues; (ii) 1 to less than 30 mole percent of 1,4-cyclohexanedimethanol residues, and (iii) 1.5 to 6 mole percent diethylene glycol residues The remainder of the diol component is (iv) an ethylene glycol residue, and (v) containing 0 to 20 mole % of at least one modifying glycol residue; and (c) a catalytic system residue comprising: 2 to 15 ppm titanium, 50 to 150 ppm antimony, and 2 to 90 ppm phosphorus Including, the total mole percent of the dicarboxylic acid component is 100 mole percent, and the total mole percent of the diol component is 100 mole percent; the concentration of the catalyst system residue is based on the weight of the polyester; The polyester has an intrinsic viscosity of 0.68 to 0.75 dL / g when measured in 60 / 40 (wt / wt) phenol / tetrachloroethane at 25° C. and a concentration of 0.5 g / dL, and the polyester is measured using a Thermal Analyst Instrument TA DSC 2920 A crystallizable film having a Tg of 72°C to 77°C as measured using a scanning rate of 20°C / min.

20. the titanium tetraalkoxide is titanium tetraisopropoxide, titanium tetraethoxide, or titanium tetrabutoxide; or the tetraalkyl titanate is tetraisopropyl titanate, or The phosphate ester is a trialkyl phosphate, an alcohol phosphate, a triphenyl phosphate, or a trisnonylphenyl phosphite.

15. The catalyst system of claim 14.

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